Amine functionalized polymers and methods of preparation
11555107 · 2023-01-17
Inventors
- Laurel L. Schafer (Vancouver, CA)
- Savvas G. Hatzikiriakos (Surrey, CA)
- Mitchell R. Perry (Vancouver, CA)
- Damon J. Gilmour (Vancouver, CA)
- Tanja Tomkovic (Vancouver, CA)
Cpc classification
B01J2540/40
PERFORMING OPERATIONS; TRANSPORTING
C08F2810/40
CHEMISTRY; METALLURGY
B01J31/1616
PERFORMING OPERATIONS; TRANSPORTING
C07C275/28
CHEMISTRY; METALLURGY
C08F210/16
CHEMISTRY; METALLURGY
C08F210/16
CHEMISTRY; METALLURGY
B01J31/2404
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/4211
PERFORMING OPERATIONS; TRANSPORTING
C07C209/60
CHEMISTRY; METALLURGY
B01J31/2243
PERFORMING OPERATIONS; TRANSPORTING
C08L23/36
CHEMISTRY; METALLURGY
International classification
B01J31/16
PERFORMING OPERATIONS; TRANSPORTING
C08F210/16
CHEMISTRY; METALLURGY
Abstract
This application pertains to amine-functionalized polymers by ring-opening metathesis (ROMP) of amine functionalized cycloalkenes.
Claims
1. An amine-functionalized compound of Formula 2: ##STR00053## wherein is a single bond or a double bond; wherein each of M.sup.1 and M.sup.2 independently is —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, or a functional end-group suitable for ring opening metathesis polymerization; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4 and the remainder of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group provided that at least one of R.sup.3 and R.sup.4 is not H, or wherein R.sup.3 and R.sup.4 are linked to form a cyclic moiety, or wherein one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; and wherein n is a natural number greater than 2, wherein the repeat units in the parenthesis in Formula 2 are connected in a head to head fashion, head to tail fashion, tail to tail fashion, or any combination thereof.
2. The amine-functionalized compound of claim 1, wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H.
3. The amine-functionalized compound of claim 1, wherein each of R.sup.1 and R.sup.2 is H.
4. The amine-functionalized compound of claim 1, wherein one of R.sup.3 and R.sup.4 is H.
5. The amine-functionalized compound of claim 1, wherein the compound is a polyalkane of Formula 5: ##STR00054## wherein each of M.sup.1 and M.sup.2 is independently —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, or a functional end-group suitable for ring opening metathesis polymerization; wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Z.sup.1, and Z.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein each of R.sup.a, R.sup.b, R.sup.c, and R.sup.d is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group provided that at least one of R.sup.a and R.sup.b is not H, or wherein R.sup.b and R.sup.a are linked to form a cyclic moiety, or wherein one of R.sup.a and R.sup.b is linked with one of R.sup.c and R.sup.d to form a cyclic moiety; wherein n is a natural number greater than 2; and wherein the repeat units in the parenthesis are connected in a head to head fashion, a head to tail fashion, a tail to tail fashion, or any combination thereof.
6. The polyalkane of claim 5, wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H.
7. The polyalkane of claim 5, wherein each of R.sup.c and R.sup.d is H.
8. The polyalkane of claim 5, wherein one of R.sup.b and R.sup.a is H.
9. The amine-functionalized compound of claim 1, wherein is a single bond.
10. A polymer comprising monomer units of the formulae: ##STR00055## wherein is a single bond or a double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4 and the remainder of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group provided that at least one of R.sup.3 and R.sup.4 is not H, or wherein R.sup.3 and R.sup.4 are linked to form a cyclic moiety, or wherein one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety; wherein in each monomer unit, r=0 or 1 and q=0 or 1, wherein in each monomer unit r+q=0, 1, or 2; wherein n and m are natural numbers; wherein n is greater than 2; and wherein the repeat units in the parenthesis are connected in a head to head fashion, a head to tail fashion, a tail to tail fashion, or any combination thereof.
11. The polymer of claim 10, wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H.
12. The polymer of claim 10, wherein each of R.sup.1 and R.sup.2 is H.
13. The polymer of claim 10, wherein one of R.sup.3 and R.sup.4 is H.
14. The polymer of claim 10 that is an amine functionalized polyalkene or polyalkane, wherein the polyalkene or polyalkane comprises: ##STR00056## ##STR00057## ##STR00058## wherein n is a natural number greater than 2.
15. The polymer of claim 10, wherein is a single bond.
16. A polymer comprising monomer units of the formulae: ##STR00059## wherein is a single bond or a double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4 and the remainder of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group provided that at least one of R.sup.3 and R.sup.4 is not H, or wherein R.sup.3 and R.sup.4 are linked to form a cyclic moiety, or wherein one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; wherein n and m are natural numbers; wherein n is greater than 2; and wherein the repeat units in the parenthesis are connected in a head to head fashion, a head to tail fashion, a tail to tail fashion, or any combination thereof.
17. The polymer of claim 16, wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H.
18. The polymer of claim 16, wherein each of R.sup.1 and R.sup.2 is H.
19. The polymer of claim 16, wherein one of R.sup.3 and R.sup.4 is H.
20. The polymer of claim 16, wherein is a single bond.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In drawings which illustrate embodiments of the invention,
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DETAILED DESCRIPTION
Definitions
(32) “Catalyst”, as used herein, refers to a chemical compound that accelerates a chemical reaction without itself being affected. “Catalyst” may be used interchangeably with terms such as “pre-catalyst”, “catalyst system”, or “catalytic system”. “Catalyst”, as used herein, includes catalytic intermediates or species formed in situ.
(33) “Group 5 metal” as used herein, refers to the d-electron comprising transition metals listed in the periodic table of the elements as group 5, including transition metals vanadium (V), niobium (Nb), tantalum (Ta), and dubnium (Db).
(34) “Hydroaminoalkylation”, as used herein, refers to a reaction between a secondary amine containing moiety and an olefin. A catalyst may often be used to promote such reaction.
(35) “Secondary amine”, as used herein, refers to an amine in which the amino group is directly bonded to two C-atoms of any hybridization. The two C-atoms in α-position to the N-atom may be sp.sup.3 hybridized.
(36) “Olefin” or “alkene”, as used herein, refers to an unsaturated hydrocarbon containing one or more pairs of C-atoms linked by a double bond.
(37) “TOF”, as used herein, refers to “turnover frequency”.
(38) Numeric ranges are inclusive of the numbers defining the range. The word “comprising” is used herein as an open-ended term, substantially equivalent to the phrase “including, but not limited to”, and the word “comprises” has a corresponding meaning. As used herein, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a thing” includes more than one such thing. Citation of references herein is not an admission that such references are prior art to an embodiment of the present invention. The invention includes all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings. Titles, headings, or the like are provided to enhance the reader's comprehension of this document, and should not be read as limiting the scope of the present invention.
(39) Amine-Functionalized Cycloalkenes
(40) This disclosure pertains to amine-functionalized cycloalkenes of Formula 1:
(41) ##STR00012##
(42) wherein: X.sup.1, X.sup.2, X.sup.3, and X.sup.4 independently are H or CH.sub.3; Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 are each independently: H; a substituted or unsubstituted linear or cyclic alkyl or alkenyl; a substituted or unsubstituted aryl; a substituted or unsubstituted heterocycle; an amine-compatible protection group; —C(═O)R′; or —C(OR′)R″; wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; and wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2.
(43) Each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.3 and R.sup.4 are linked to form a cyclic moiety, wherein each of R.sup.1 and R.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety in which case each of remaining groups of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(44) In various embodiments of the amine-functionalized cycloalkenes, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments of the amine-functionalized cycloalkenes, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments of the amine-functionalized cycloalkenes, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments of the amine-functionalized cycloalkenes, at least one of R.sup.1 and R.sup.2 is H. In various embodiments of the amine-functionalized cycloalkenes, at least one of R.sup.3 and R.sup.4 is H.
(45) In various embodiments of the amine-functionalized cycloalkenes, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, at least one ring-carbon atom adjacent to the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is substituted with two H atoms. In various embodiments, Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, and: each Y.sup.1 and Y.sup.2 is H; each of Y.sup.5 and Y.sup.6 is H; or each of each Y.sup.1, Y.sup.2, Y.sup.5, and Y.sup.6 is H.
(46) In various embodiments of the amine-functionalized cycloalkenes, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is further substituted with a hydrogen atom. In various embodiments, Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4 and Y.sup.4 is H.
(47) This disclosure further pertains to polymers prepared by the ring opening metathesis polymerization (ROMP) of an amine-functionalized cycloalkene as described above.
(48) This disclosure further pertains to polymers prepared by the ring opening metathesis polymerization (ROMP) of a mixture of different amine-functionalized cycloalkenes as described above. In various embodiments, the mixture comprises amine-functionalized cycloalkenes that are regioisomers. In various embodiments, the position of —CR.sup.1R.sup.2—NR.sup.3R.sup.4 groups on adjacent carbons is swapped between regioisomers.
(49) In various embodiments, the monomer units are polymerized head-to-head, head-to-tail, tail-to-tail, or any combination thereof.
(50) In various embodiments, the polymer is hydrogenated to remove double bonds in the polymer.
(51) In various embodiments, the polymer has self-healing properties. In various embodiments, the polymer has adhesive properties. In various embodiments, the polymer has antimicrobial activity.
(52) Polymers as described above may be useful as antimicrobial agents. Polymers as described above may be useful for reducing fouling. Fouling may include biofouling. Polymers as described above may be useful as adhesive agents. The adhesive agent may for adhering to a substrate. The substrate may be Teflon, glass, or metal.
(53) Polymers as described above may be useful as a coating, a compatibilizer, a stabilizer, metal scavenger, a membrane a gasket, an anticoagulant, a drug delivery agent, or a scavenger agent. In various embodiments, the scavenger agent is for binding pollutants during environmental remediation in marine environments. In various embodiments, the pollutants include oil, plastic particles, or a combination thereof. In various embodiments the membrane is an electrolyte membrane or a filtering membrane for water purification.
(54) Amine-Functionalized Compounds
(55) This disclosure further pertains to amine-functionalized compounds of Formula 2:
(56) ##STR00013## wherein indicates an optional double bond; wherein each of M.sup.1 and M.sup.2 is independently —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, or a functional end-group suitable for ring opening metathesis polymerization; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; and wherein n is a natural number.
(57) Each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.3 and R.sup.4 are linked to form a cyclic moiety, wherein each of R.sup.1 and R.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety in which case each of remaining groups of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(58) In various embodiments, the monomer units forming the amine-functionalized compound of Formula 2 are connected head to tail, head to head, tail to tail, or any combination thereof.
(59) In various embodiments, n is in the range of 3 to 1000. In various embodiments, n is in the range of 3 to 1000. In various embodiments, n is in the range of 3 to 600. In various embodiments, n is in the range of 5 to 400.
(60) In various embodiments, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments, at least one of R.sup.1 and R.sup.2 is H. In various embodiments, at least one of R.sup.3 and R.sup.4 is H.
(61) In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR3R4, at least one ring-carbon atom adjacent to the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is substituted with two H atoms. For example, where Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4: each Y.sup.1 and Y.sup.2 is H; each of Y.sup.5 and Y.sup.6 is H; or each of each Y.sup.1, Y.sup.2, Y.sup.5, and Y.sup.6 is H.
(62) In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is further substituted with a hydrogen atom. For example, where Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, Y.sup.4 is H.
(63) Amine-functionalized compounds as described above may be useful as antimicrobial agents. Amine-functionalized compounds as described above may be useful for reducing fouling. Fouling may include biofouling. Amine-functionalized compounds as described above may be useful as adhesive agents. The adhesive agent may for adhering to a substrate. The substrate may be Teflon, glass, or metal.
(64) Amine-functionalized compounds as described above may be useful as a coating, a compatibilizer, a stabilizer, metal scavenger, a membrane a gasket, an anticoagulant, a drug delivery agent, or a scavenger agent. In various embodiments, the scavenger agent is for binding pollutants during environmental remediation in marine environments. In various embodiments, the pollutants include oil, plastic particles, or a combination thereof. In various embodiments the membrane is an electrolyte membrane or a filtering membrane for water purification.
(65) Polymers of Formulae 3, 4, and 7
(66) This disclosure further pertains to polymers comprising an oligomer of Formula 3:
(67) ##STR00014## wherein indicates an optional double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; wherein n and m are natural numbers; and wherein the monomers are connected in a head to head fashion.
(68) This disclosure further pertains to polymers comprising an oligomer of Formula 4:
(69) ##STR00015## wherein indicates an optional double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; wherein n and m are natural numbers; and wherein the monomers are connected in a tail to tail fashion.
(70) This disclosure further pertains to polymers comprising an oligomer of Formula 7:
(71) ##STR00016## wherein indicates an optional double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; wherein n and m are natural numbers; and wherein the monomers are connected in a head to tail fashion.
(72) For oligomers of Formulae 3, 4, and 7, each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.3 and R.sup.4 are linked to form a cyclic moiety, wherein each of R.sup.1 and R.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety in which case each of remaining groups of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(73) While Formulae 3, 4, and 7 currently specify that the monomers are connected in a head to tail fashion, head to head fashion, or a tail to tail fashion, as the case may be, the skilled person will understand that the monomers could be connected in any combination thereof.
(74) In various embodiments of polymers comprising an oligomer of Formulae 3, 4, and 7, n+m is in the range of 3 to 1000. In various embodiments, n is in the range of 3 to 1000. In various embodiments, n+m is in the range of 3 to 600. In various embodiments, n+m is in the range of 5 to 400.
(75) In various embodiments of polymers comprising an oligomer of Formulae 3, 4, and 7, the polymer is capped with —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, a functional end-group suitable for ring opening metathesis polymerization, or any combination thereof.
(76) In various embodiments of polymers comprising an oligomer of Formulae 3, 4, and 7, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments of polymers of Formulae 3 and 4, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments of polymers of Formulae 3 and 4, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments of polymers of Formulae 3 and 4, at least one of R.sup.1 and R.sup.2 is H. In various embodiments of polymers of Formulae 3 and 4, at least one of R.sup.3 and R.sup.4 is H.
(77) In various embodiments of polymers comprising an oligomer of Formulae 3, 4, and 7, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, at least one ring-carbon atom adjacent to the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is substituted with two H atoms. For example, when Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4: each Y.sup.1 and Y.sup.2 is H; each of Y.sup.5 and Y.sup.6 is H; or each of each Y.sup.1, Y.sup.2, Y.sup.5, and Y.sup.6 is H.
(78) In various embodiments of polymers comprising an oligomer of Formulae 3, 4, and 7, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is further substituted with a hydrogen atom. For example, where Y.sup.3 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, Y.sup.4 is H.
(79) In various embodiments, the polymer has self-healing properties. In various embodiments, the polymer has adhesive properties. In various embodiments, the polymer has antimicrobial activity.
(80) Aspects of the disclosure also pertain to block copolymers prepared by ring opening metathesis polymerization of: an amine-functionalized cycloalkene as described above; and at least one additional cycloalkene. The at least one additional cycloalkene includes norbornene or an arylamine substituted norbornene.
(81) Aspects of the disclosure also pertain to block copolymers comprising: an amine functionalized compound as described above; and a polymer formed by radical or anionic polymerization, for which the functional end-group M of the amine functionalized compound serves as an initiation point.
(82) Aspects of the disclosure also pertain to brush copolymers comprising a polymer as described above and polymeric bristles or brushes, wherein at least one of X.sup.1, X.sup.2, X.sup.3, X.sup.4, Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, R′, R″, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 serves as an initiation point for subsequent synthesis of polymeric bristles or brushes.
(83) Aspects of the disclosure also pertain to random copolymers prepared by ring opening metathesis polymerization of: an amine-functionalized cycloalkene as described above; and at least one additional cycloalkene. The at least one additional cycloalkene includes norbornene or an arylamine substituted norbornene.
(84) Polymers as described above may be useful as antimicrobial agents. Polymers as described above may be useful for reducing fouling. Fouling may include biofouling. Polymers as described above may be useful as adhesive agents. The adhesive agent may for adhering to a substrate. The substrate may be Teflon, glass, or metal.
(85) Polymers as described above as described above may be useful as a coating, a compatibilizer, a stabilizer, metal scavenger, a membrane a gasket, an anticoagulant, a drug delivery agent, or a scavenger agent. In various embodiments, the scavenger agent is for binding pollutants during environmental remediation in marine environments. In various embodiments, the pollutants include oil, plastic particles, or a combination thereof. In various embodiments the membrane is an electrolyte membrane or a filtering membrane for water purification.
(86) Amine Functionalized Polyalkenes and Polyalkanes
(87) Aspects of the disclosure also pertain to an amine functionalized polyalkene or polyalkane, wherein the polyalkene or polyalkane comprises:
(88) ##STR00017## ##STR00018## ##STR00019##
(89) wherein n is a natural number greater than 1.
(90) In various embodiments, n is in the range of 3 to 1000. In various embodiments, n is in the range of 3 to 600. In various embodiments, n is in the range of 5 to 400.
(91) Aspects of the disclosure also pertain to polyalkanes of Formula 5:
(92) ##STR00020## wherein each of M.sup.1 and M.sup.2 independently is —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, or a functional end-group suitable for ring opening metathesis polymerization; wherein each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Z.sup.1, and Z.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; and wherein n is a natural greater than 1.
(93) Each of R.sup.a, R.sup.b, R.sup.c, and R.sup.d is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.b and R.sup.a are linked to form a cyclic moiety, wherein each of R.sup.c, and R.sup.d is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.a and R.sup.b is linked with one of R.sup.c and R.sup.d to form a cyclic moiety in which case each of remaining groups of R.sup.a, R.sup.b, R.sup.c, and R.sup.d, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(94) In various embodiments, at least one of R.sup.b and R.sup.a is H. In various embodiments, one of R.sup.b and R.sup.a is H. In various embodiments, R.sup.b is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(95) In various embodiments, the monomer units forming the polyalkanes of Formula 5 are connected head to tail, head to head, tail to tail, or any combination thereof.
(96) In various embodiments, n is in the range of 3 to 1000. In various embodiments, n is in the range of 3 to 600. In various embodiments, n is in the range of 5 to 400.
(97) In various embodiments, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments, at least one of R.sup.1 and R.sup.2 is H. In various embodiments, at least one of R.sup.3 and R.sup.4 is H.
(98) Aspects of the disclosure pertain to co-polymers of Formula X:
(99) ##STR00021## wherein indicates an optional double bond; wherein each of M.sup.1 and M.sup.2 is independently —OH, a substituted or unsubstituted C.sub.1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle, or a functional end-group suitable for ring opening metathesis polymerization; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7, Y.sup.8, Y.sup.9, Y.sup.10, Y.sup.11, Y.sup.12, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2; and wherein n and m are natural numbers; and
(100) Each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.3 and R.sup.4 are linked to form a cyclic moiety, wherein each of R.sup.1 and R.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety in which case each of remaining groups of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(101) In various embodiments, the monomer units forming the co-polymers of Formula X are connected head to tail, head to head, tail to tail, or any combination thereof. In various embodiments, the monomer units are connected in a head to head fashion.
(102) In various embodiments of polymers of Formulae X, n+m is in the range of 3 to 1000. In various embodiments, n+m is in the range of 3 to 600. In various embodiments, n+m is in the range of 5 to 400.
(103) In various embodiments, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments, at least one of R.sup.1 and R.sup.2 is H. In various embodiments, at least one of R.sup.3 and R.sup.4 is H. In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, at least one ring-carbon atom adjacent to the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is substituted with two H atoms. In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is further substituted with a hydrogen atom.
(104) Aspects of the disclosure pertain to co-polymers comprising a mixture of different amine-functionalized monomer units of Formula 6:
(105) ##STR00022## wherein indicates an optional double bond; wherein each X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is independently H or CH.sub.3; wherein each Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, —C(═O)R′, or —C(OR′)R″, and wherein at least one of Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4; wherein each of R′ and R″ is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; and wherein r=0 or 1 and q=0 or 1, wherein r+q=0, 1, or 2.
(106) Each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Alternatively, R.sup.3 and R.sup.4 are linked to form a cyclic moiety, wherein each of R.sup.1 and R.sup.2 is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group. Yet alternatively, one of R.sup.3 and R.sup.4 is linked with one of R.sup.1 and R.sup.2 to form a cyclic moiety in which case each of remaining groups of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, as the case may be, is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group.
(107) In various embodiments, the monomer units of formula 6 forming the co-polymer are connected head to tail, head to head, tail to tail, or any combination thereof.
(108) In various embodiments the number of monomer units of formula 6 forming the polymer is in the range of 3 to 1000. In various embodiments the number of monomer units of formula 6 forming the polymer is in the range of 3 to 600. In various embodiments, n+m is in the range of 5 to 400.
(109) In various embodiments, each of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is H. In various embodiments, only one of X.sup.1, X.sup.2, X.sup.3, and X.sup.4 is CH.sub.3. In various embodiments, each of X.sup.1 and X.sup.3 is H and each of X.sup.2 and X.sup.4 is CH.sub.3. In various embodiments, at least one of R.sup.1 and R.sup.2 is H. In various embodiments, at least one of R.sup.3 and R.sup.4 is H. In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, at least one ring-carbon atom adjacent to the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is substituted with two H atoms. In various embodiments, when Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Z.sup.1, Z.sup.2, Z.sup.3, or Z.sup.4 is —CR.sup.1R.sup.2—NR.sup.3R.sup.4, the ring-carbon atom substituted with —CR.sup.1R.sup.2—NR.sup.3R.sup.4 is further substituted with a hydrogen atom.
(110) Various polyalkene or polyalkanes as described above may be useful as an antimicrobial agent. Various polyalkene or polyalkanes as described above may be useful for reducing fouling. Fouling may include biofouling. Various polyalkene or polyalkanes as described above may be useful as an adhesive agent. The adhesive agent may for adhering to a substrate. The substrate may be Teflon, glass, or metal.
(111) Various polyalkene or polyalkanes as described above may be useful as a coating, a compatibilizer, a stabilizer, metal scavenger, a membrane a gasket, an anticoagulant, a drug delivery agent, or a scavenger agent. In various embodiments, the scavenger agent is for binding pollutants during environmental remediation in marine environments. In various embodiments, the pollutants include oil, plastic particles, or a combination thereof. In various embodiments the membrane is an electrolyte membrane or a filtering membrane for water purification.
(112) Substrates
(113) Aspects of the disclosure pertain to a substrate coated with a polyalkene or polyalkane, amine-functionalized compound, or polymer as described above.
(114) In various embodiments, the substrate reduces biofouling.
(115) Methods of Preparing Polymers
(116) The novel amine-containing polymers disclosed herein are enabled by the presently developed and disclosed catalytic synthesis using a combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP) using Grubbs second generation catalyst (“G2”). This preparation transforms commercially available starting materials to a rich and diverse class of novel polymers without the use of additives or directing/protecting groups, thereby minimizing waste generation. The development of this atom-economic, gram-scale preparation was conducted for a series of secondary aryl-amine containing cyclooctene derivatives. The preparation of such amine-functionalized polyethylene analogs comprises two, and optionally three, steps. First, monomers are synthesized by the catalytic hydroaminoalkylation of a cycloalkene, e.g. cyclooctadiene, an alkene aminoalkylation reaction that proceeds in an atom-economic fashion. This methodology avoids amine directing or protecting groups (see
(117) Aspects of the disclosure pertain to methods of preparing polyalkanes of Formula 5 as defined above, methods of preparing amine-functionalized compounds as defined above, methods of preparing a polyalkene or polyalkane of as defined above, or methods of preparing a polymer comprising an oligomer of Formula 3, Formula 4, or Formula 7 as defined above. These methods comprise: (i) contacting a cycloalkene with a secondary amine containing moiety in the presence of a group 5 metal based catalytic complex to obtain a hydroaminoalkyl-substituted cycloalkene; (ii) performing ring-opening metastasis polymerization of said hydroaminoalkyl-substituted cycloalkene to obtain an amine-functionalized polyalkene; and, optionally, (iii) hydrogenating said amine-functionalized polyalkene from step (ii) to obtain the amine-functionalized polyalkane of Formula 5, the polyalkene, polyalkane, or polymer as the case may be.
(118) Aspects of the disclosure further pertain to a method of preparing an amine-functionalized cycloalkene of Formula 1, said method comprising: (i) contacting a cycloalkene with a secondary amine containing moiety in the presence of a group 5 metal based catalytic complex to obtain a hydroaminoalkyl-substituted cycloalkene.
(119) In various embodiments of the methods described above, the secondary amine-containing moiety comprises at least two α-sp.sup.3 hybridized C—H bonds. In various embodiments, the secondary amine-containing moiety is a C.sub.4-C.sub.100 linear, branched, or cyclic alkyl, optionally substituted and/or comprising heterotaoms. In various embodiments, the secondary amine-containing moiety is substituted with a halogen, an ether, another amine, an alkyl, an alkene, an acetal, a phosphine, an amide, an alkyne, an imine, a nitrile, an isocyanide, an epoxide, a boronic acid ester; a phenyl that optionally may be substituted and/or part of a condensed ring system, or any combination thereof. In various embodiments, the secondary amine-containing moiety is: pyrrolidine; piperidine;
(120) ##STR00023##
(121) wherein Z is H, OCF.sub.3, F, Cl, Br, I, or OCH.sub.3. In various embodiments, the secondary amine-containing moiety is:
(122) ##STR00024##
(123) Cycloalkenes
(124) In various embodiments of the methods disclosed above, the cycloalkene contacted with the secondary amine containing moiety is cyclooctadiene. However, the skilled person would understand other cycloalkenes could be used in the context of this disclosure.
(125) Catalyst Complexes
(126) In various embodiments of the methods disclosed above, the group 5 metal based catalytic complex has the structure of Formula I:
(127) ##STR00025## wherein: R.sup.5 and R.sup.6 are: each independently: H; a C.sub.1-C.sub.40 substituted or unsubstituted linear, branched or cyclic alkyl or alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or bonded together thereby forming, together with the nitrogen atom they are both bound to, a heterocycle; R.sup.7: is H; a C.sub.1-C.sub.40 substituted or unsubstituted linear, branched or cyclic alkyl or alkenyl or alkynyl; or a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or bonded together with R.sup.5 and/or R.sup.6 to form a heterocycle. M is a group 5 metal; a=0 to 4 and b=0 to 4, wherein the sum of a and b is 4; each X is a halogen substituent; each R.sup.8 is independently: H; or a C.sub.1-C.sub.20 substituted or unsubstituted, linear, branched or cyclic alkyl, optionally comprising heteroatoms. In various embodiments, each X is independently Cl or Br. In various embodiments, a=1 or a=2.
(128) In various embodiments, R.sup.5 and R.sup.6 are each independently: methyl; ethyl; isopropyl; cyclohexyl; phenyl; 2,6-dimethyl phenyl; 2,4,6-trimethyl phenyl; 4-methyl phenyl; optionally substituted piperidine; optionally substituted pyrrolidine; or substituted morpholine.
(129) In various embodiments, R.sup.5 and R.sup.6 are bonded together to form, together with the nitrogen atom they are both bound to, a 6-membered ring, which optionally may be substituted.
(130) In various embodiments: R.sup.5 and R.sup.6 are each phenyl; R.sup.5 is phenyl and R.sup.6 is isopropyl; R.sup.5 and R.sup.6 are bonded together to form, together with the nitrogen atom they are both bound to, piperidinyl; R.sup.5 is phenyl and R.sup.6 is methyl; R.sup.5 is methyl and R.sup.6 is 1-phenylethyl; R.sup.5 is methyl and R.sup.6 is isopropyl; or R.sup.5 is phenyl and R.sup.6 is diphenylmethyl.
(131) In various embodiments, R.sup.7 is: phenyl; 2,6-dimethyl phenyl; 2,6-di(isopropyl) phenyl; or
(132) ##STR00026##
(133) In various embodiments, R.sup.7 is bonded together with R.sup.5 and/or R.sup.6 to form, together with each of the nitrogen atoms they are bound to, a 5-membered ring, which optionally may be substituted. R.sup.7 is bonded together with R.sup.5 and/or R.sup.6, and each of the nitrogen atoms they are bound to, to form:
(134) ##STR00027##
(135) In various embodiments, R.sup.8 is —CH.sub.3, —NMe.sub.2, —CH.sub.2C(CH.sub.3).sub.3, or —CH.sub.2Si(CH.sub.3).sub.3.
(136) In various embodiments, M is tantalum (Ta), niobium (Nb), or vanadium (V).
(137) In various embodiments of the methods disclosed above, the group 5 metal based catalytic complex has the structure of Formula II
(138) ##STR00028## wherein: R.sup.5 and R.sup.6 are: each independently: methyl; ethyl; isopropyl; cyclohexyl; phenyl; 2,6-dimethyl phenyl; 2,4,6-trimethyl phenyl; 4-methyl phenyl; optionally substituted piperidine; optionally substituted pyrrolidine; or substituted morpholine; or bonded together to form, together with the nitrogen atom they are both bound to, a 6-membered ring, which optionally may be substituted; R.sup.7 is: phenyl; 2,6-dimethyl phenyl; or 2,6-di(isopropyl) phenyl; or bonded together with R.sup.5 and/or R.sup.6 to form, together with each of the nitrogen atoms they are bound to, a 5-membered ring, which optionally may be substituted; each X is independently Cl or Br; a=1 or 2 and b=(4−a); and R.sup.8 is —CH.sub.3, —NMe.sub.2, —CH.sub.2C(CH.sub.3).sub.3, or —CH.sub.2Si(CH.sub.3).sub.3.
(139) In various embodiments, the group 5 metal based catalytic complex is:
(140) ##STR00029##
(141) The reaction conditions may include a reaction temperature in the range from 50° C. to 200° C., a reaction temperature in the range from 75° C. to 165° C., a reaction temperature in the range from 90° C. to 150° C., a reaction temperature in the range from range from 110° C. to 130° C., a reaction temperature of about 110° C., or a reaction temperature of about 130° C.
(142) The reaction conditions may include a solvent. The solvent may be non-protic. The solvent may be toluene, benzene, or a mixture thereof.
(143) The secondary amine-containing moiety and said cycloalkene may be provided in a stoichiometric ratio from 0.1 to 1.5. The secondary amine-containing moiety and said cycloalkene may be provided in a stoichiometric ratio of about 1:1.
EXAMPLES
(144) Various alternative embodiments and examples are described herein. These embodiments and examples are illustrative and should not be construed as limiting the scope of the invention. In particular, while tantalum was used as the representative group 5 metal for these studies, the skilled person will expect other group 5 metals, and especially niobium, to perform similarly.
(145) Materials and Methods
(146) The procedures described herein are given for the purposes of example and illustration only and should not be considered to limit the spirit or scope of the invention.
1. General
(147) All reactions were performed under an inert atmosphere using a Schlenk double manifold equipped with N.sub.2 and high vacuum (10.sup.−3 mbar) or a glovebox filled with N.sub.2. All glassware used was heated above 160° C. in an oven prior to use. Reactions were performed in threaded 20 mL scintillation vials equipped with a Teflon-coated magnetic stir bar and a Teflon-lined polypropylene screw-cap. Toluene and hexane were purified by passing over activated alumina columns prior to collection and storage in the glovebox. Thin layer chromatography (TLC) was performed on EMD Silica gel 60 F254 plates and visualized under a 254 nm UV light. Flash chromatography was performed using an automated Biotage purification system using SilicaFlash F60 silica gel (230-400 mesh) (Silicycle) as a stationary phase and ACS grade Flexanes/Ethyl Acetate as a mobile phase.
2. Reagents
(148) All reagents were purchased from commercial sources. 3-methyl 2-pyridone (Combi-blocks) was purified by sublimation. Cyclooctadiene (Aldrich), N-methyl aniline (Aldrich), 4-fluoro N-methyl aniline (Aldrich), and 4-bromo N-methyl aniline (Oakwood) were stirred over CaH.sub.2 for a minimum of 2 h, separated by distillation, then manipulated using standard Schlenk techniques. 4-methoxy N-methyl aniline was prepared as according to literature and purified via sublimation. [TaCl.sub.2(NMe.sub.2).sub.3] and Chlorotris(dimethylamido)(κ.sup.2-N,O-3-methyl-2-pyridonato)tantalum(V) were prepared as per literature precedent. Grubbs Catalyst™ 2nd Generation (Sigma-Aldrich) was purchased and used without further purification.
3. Instrumentation
(149) NMR Spectroscopy. .sup.1H NMR spectra were recorded on Bruker 300 MHz, or 400 MHz, Avance spectrometers at ambient temperature at 293 K. .sup.13C and .sup.19F NMR spectra were recorded on a Bruker Avance 300 instrument at 293 K. Chemical shifts (δ) are reported in parts per million (ppm). Coupling constants J are given in Hertz (Hz). The following abbreviations are used to indicate signal multiplicity: s=singlet; d=doublet; dd=doublet of doublets; t=triplet; q=quartet; m=multiplet; br=broad; appt=apparent. Assignment of the signals was carried out using 1D (.sup.1H, .sup.13C{.sup.1H}) and 2D (COSY, HSQC and HMBC) NMR experiments.
(150) Infrared (IR) Spectroscopy. Spectra were recorded at room temperature on a Perkin Elmer FTIR equipped with an ATR accessory for direct measurement on oils and polymeric materials. Bands are reported in wavenumbers (cm.sup.−1) and assigned with the abbreviations s=strong, m=medium, w=weak, sh=shoulder, br=broad.
(151) Gel Permeation Chromatography. Polymer M.sub.n, M.sub.w and dispersity () were obtained using triple detection gel permeation chromatography (GPC) using a Waters liquid chromatograph equipped with an Agilent 1200 series isocratic pump and autosampler, Phenomenex Phenogel 5 μm narrow bore columns, Wyatt OptilabEx differential refractometer, Wyatt tristar miniDAWN (laser light scattering detector) and a Wyatt ViscoStar viscometer. A flow rate of 0.5 ml.Math.min-1 was used and samples were dissolved in THF (˜2 mg.Math.ml.sup.−1). The measurements were carried out at a laser wavelength of 690 nm, at 25° C. The data was analyzed using the Astra® processing program provided by Wyatt Technology Corp.
(152) Differential Scanning Calorimetry (DSC). DSC was done on a TA Instruments DSC Q2000 equipped with a TA Instruments Refrigerated Cooling System 90. A heating/cooling rate of 5° C./min was used for each run in the range of −90° C. to 120° C. Duplicate runs were measured after the completion of one heating/cooling cycle to remove thermal history.
(153) Thermogravimetric Analysis (TGA). A thermogravimetric analyzer, model Shimadzu TGA-60, was used for TG measurements of the samples. A small amount (3-5 mg) was analyzed using the alumina crucible. The samples were pre-heated at 105° C. for 15 min in the TGA furnace to remove moisture. Then, the samples were tested from 30° C. to 600° C. at a rate of 10° C./min under the nitrogen atmosphere.
(154) Rheological Measurements. Rheological characterization was conducted using the Anton Paar MCR 702 rotational rheometer, equipped with a cone-partitioned-plate geometry. The main advantage of this geometry is the elimination of the edge fracture.sup.29. The top part of this type of geometry contains an 8 mm in diameter plate attached to the transducer (center plate), and a coaxial stationary ring (partitioned plate, 25 mm in diameter), which acts as a shield and prevents edge fracture of the sample. The bottom plate is 25 mm in diameter with an angle of 0.07 rad. The experiments were performed at distance gap of 51 μm.
(155) The thermal stability of the samples was monitored isothermally for 2 hrs by applying the frequency of 0.1 Hz and shear strain of 0.01. An initial strain sweep test at the frequency of 0.1 Hz was used to determine the threshold of the linear viscoelastic region. Frequency sweep experiments (0.01-100 Hz) at a fixed shear strain of 0.01 were performed at different temperatures, which allows using the time-temperature superposition principle (tTS) and generating the master curve for each sample at the reference temperatures. Experiments were conducted in triplicate, and representative data is presented.
4. Synthesis and Results
(156) General methods of synthesizing Group V metal catalyst complexes useful in the context of the present disclosure, including Chlorotris(dimethylamido)(κ2-N,O-3-methyl-2-pyridonato)tantalum(V), are described in international patent application no. PCT/CA2018/050619, which published as WO 2018/213938, the contents of which are incorporated herein by reference.
4.1 Chlorotris(dimethylamido)(κ.SUP.2.-N,O-3-methyl-2-pyridonato) tantalum(V)
(157) ##STR00030##
(158) To a suspension of [TaCl.sub.2(NMe.sub.2).sub.3].sub.2 (0.23 g, 0.3 mmol) in toluene (˜2 mL) was added a suspension of sodium 3-methyl-2-pyridonate (0.075 g, 0.6 mmol) in toluene (˜2 mL) at room temperature. Upon stirring overnight, the initially yellow, cloudy mixture became an orange, clear solution. Volatiles were removed in vacuo to give 0.250 g orange-brown oil (90%). The crude residue was dissolved in 1.0 g toluene solvent (0.25 w/w %) and used for hydroaminoalkylation (HAA). .sup.1H NMR (400 MHz, d.sub.8-tol): δ 8.23 (d of d, 1H, ArH), δ 6.83 (d, 1H, ArH), δ 6.20 (t, 1H, ArH), δ 3.75-3.53 (br s, 18H, (NCH.sub.3).sub.2).sub.3) δ 2.10 (s, 3H, CH.sub.3). Characterization was consistent with previously reported values.
4.2 Hydroaminoalkylation Reaction
(159)
(160) Referring to
(161) (Z)—N-(cyclooct-4-en-1-ylmethyl)aniline (amine-functionalized cycloalkene “M1”). To a solution of Chlorotris(dimethylamido)(κ.sup.2-N,O-3-methyl-2-pyridonato)tantalum(V) (200 mg, 5 mol %) in toluene (˜3 mL) was added N-methyl aniline (1 g, 9.34 mmol) followed by cyclooctadiene (1.54 g, 14 mmol). The initially orange, cloudy solution was equipped with a stirring bar, capped, removed from the glovebox, and heated to 145° C. in an oil-bath. Upon reaching temperature the reaction mixture goes dark red and was then heated with stirring for 20 h. After this time, the reaction was quenched with exposure to ambient atmosphere and the addition of 1 mL methanol. Purification was completed via automated column chromatography (0 to 20% gradient of ethyl acetate/hexanes) to afford 1.68 g of pale-yellow oil (84.0%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(162) (Z)—N-(cyclooct-4-en-1-ylmethyl)-4-fluoroaniline (amine-functionalized cycloalkene “M2”). Prepared as per M1 using 4-fluoro-N-methylaniline as the amine substrate to afford 1.53 g of pale-yellow oil (81.7%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(163) (Z)—N-(cyclooct-4-en-1-ylmethyl)-4-bromoaniline (amine-functionalized cycloalkene “M3”). Prepared as per M1 using 4-bromo-N-methyl aniline as the amine substrate to afford 1.29 g of pale-yellow oil (81.3%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(164) (Z)—N-(cyclooct-4-en-1-ylmethyl)-4-methoxyaniline (amine-functionalized cycloalkene “M4”). Prepared as per M1 using 4-methoxy N-methyl aniline as the amine substrate to afford 1.52 g of yellow oil (85.0%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(165) (Z)—N-(cyclooct-4-en-1-ylmethyl)-4-(methylthio)aniline (amine-functionalized cycloalkene “M5”). Prepared as per M1 using N-methyl-4-(methylthio)aniline (2.5 g) as the amine substrate to afford 1.52 g of yellow oil (71%).sup.1H NMR (300 MHz, CDCl.sub.3): δ 7.22 (d of d, .sup.3J=8.7 Hz, .sup.3J=2.5 Hz, 2H, 2×ArH), δ 6.54 (t, .sup.3J=8.7 Hz, 1H, ArH), δ 5.67 (m, 2H, 2×RHC═CHR), δ 3.88 (br s, 1H, NH), δ 2.93 (m, 2H, CH.sub.2), δ 2.42 (s, 3H, CH.sub.3), δ 2.38 (m, 1H, CH), δ 2.16 (m, 3H), δ 1.77-1.19 (m, 7H).sup.13C{1H} NMR (75 MHz, CDCl.sub.3): δ 146.9 (C), δ 131.5 (CH), δ 130.1 (CH), δ 124.2 (C), δ 113.6 (CH), δ 51.9 (CH.sub.2), δ 37.5 (CH.sub.2), δ 33.3 (CH.sub.2), δ 31.1 (CH.sub.2), δ 28.1 (CH), δ 25.9 (CH), δ 24.7 (CH), δ 19.2 (CH.sub.3) IR (neat oil, cm.sup.−1, int): 3417br, 3013w, 2915vs, 2850s, 1598vs, 1500vs, 1466m, 1437w, 1400w, 1367w, 1312m, 1289m, 1248m, 1201w, 1181w, 1128w, 1103w, 966w, 884w, 812m, 756w, 722m HRMS-ESI (m/z) Calcd: 262.1629; found: 262.1637.
(166) (Z)—N-(cyclooct-4-en-1-ylmethyl)-cyclohexanamine (amine-functionalized cycloalkene “M6”). Prepared as per M1 using N-methylcyclohexylamine (0.45 g) as the amine substrate to afford 0.6 g of yellow oil (53%).sup.1H NMR (300 MHz, CDCl.sub.3): δ 5.64 (m, 2H, 2×RHC═CHR), δ 2.44 (m, 3H, N—CH.sub.2, N—CH), δ 2.34 (m, 1H, CH), δ 2.12 (m, 3H), δ 1.88-1.00 (m, 18H).sup.13C{1H} NMR (75 MHz, CDCl.sub.3): δ 130.2 (CH), δ 129.9 (CH), δ 56.9 (CH), δ 54.9 (CH.sub.2), δ 38.1 (CH), δ 33.7 (CH.sub.2), δ 33.6 (CH.sub.2), δ 31.6 (CH.sub.2), δ 28.2 (CH), δ 26.2 (CH.sub.2), δ 25.9 (CH.sub.2), δ 25.1 (CH.sub.2), δ 24.9 (CH.sub.2) IR (neat oil, cm.sup.−1, int): 3014w, 2923vs, 2851s, 1651m, 1612w, 1570w, 1463s, 1449s, 1374w, 1348w, 1258w, 1228w, 1131m, 1028w, 989w, 972w, 941 w, 886m, 844w, 775m, 754m, 721vs HRMS-ESI (m/z) Calcd: 222.2222; found: 222.2228.
(167) Table 1 provides a summary of the exemplary amine-functionalized cycloalkenes synthesized.
(168) TABLE-US-00001 TABLE 1 Overview of synthesized amine-functionalized cycloalkenes. Compound ID IUPAC Name Chemical Structure M1 (Z)-N-(cyclooct-4-en-1- ylmethyl)aniline
(169) These monomers bearing pendant, secondary aryl amines were amenable to ROMP using Grubbs Catalyst 2nd Generation to obtain linear polymers.
4.3 Polymerization
(170)
(171) Poly(N-(cyclooct-4-en-1-ylmethyl)aniline) (polymer “P1”). Prepared as above to afford 0.602 g of an off-white gun-like solid (81%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(172) Poly(N-(cyclooct-4-en-1-ylmethyl)-4-fluoroaniline) (polymer “P2”). Prepared as above to afford 0.690 g of gummy, off-white solid (88%). %). .sup.1H NMR (300 MHz, CDCl.sub.3,
(173) Poly(N-(cyclooct-4-en-1-ylmethyl)-4-bromoaniline) (polymer “P3”). Prepared as above to afford 0.592 g of gummy, off-white solid (94%). .sup.1H NMR (400 MHz, CDCl.sub.3,
(174) Poly(N-(cyclooct-4-en-1-ylmethyl)-4-methoxyaniline (polymer “P4”). Prepared as above to afford 0.541 g of gummy, off-white solid (88%). .sup.1H NMR (400 MHz, CDCl.sub.3,
(175) Poly(N-(oct-4-en-1-ylmethyl)-4-(methylthio)aniline (polymer “P5”). Prepared as above to afford a dark purple solid (70%). .sup.1H NMR (300 MHz, CDCl.sub.3): δ 7.22 (m, 2H, 2×ArH), δ 6.54 (m, 2H, 2×ArH), δ 5.40 (br s, 2H, 2×RHC═CHR), δ 3.69 (br s, 1H, NH), δ 2.99 (m, 2H, CH.sub.2), δ 2.42 (m, 3H, CH.sub.3), δ 1.99 (m, 4H), δ 1.77-1.19 (m, 7H) IR (neat oil, cm.sup.−1, int): 3414br, 2917s, 2852m, 1597vs, 1500vs, 1474m, 1455m, 1435w, 1401w, 1312m, 1289m, 1250m, 1181m, 1101w, 966s, 812s, 735w.
(176) Poly(N-(oct-4-en-1-ylmethyl)-cyclohexanamine (polymer “P6”). Prepared as above to afford a dark orange solid (42%). .sup.1H NMR (300 MHz, C.sub.7D.sub.8): δ 5.53 (br s, 2H, 2×RHC═CHR), δ 2.55 (br s, 2H, CH.sub.2), δ 2.37 (m, 1H, CH), δ 2.11 (br s, 4H, CH.sub.2), δ 1.86-1.07 (m, 17H, CH, CH.sub.2), δ 0.52 (br s, 1H, NH) IR (neat oil, cm.sup.−1, int): 2921vs, 2851s, 1670w, 1449s, 1365w, 1347w, 1259w, 1241w, 1130m, 966vs, 922w, 888m, 845m, 845w, 786w, 723s.
(177) Polymers P1 to P6 were obtained in high yield (>80%) regardless of the pendant secondary amine substituent. Analysis of chemical shifts in .sup.1H NMR spectra showed broadened signals consistent with polymer formation. For example, for polymer P2 one major peak was observed in the .sup.19F NMR spectrum; a broad singlet at δ −127.7 ppm, while for polymer P4 the methoxy substituent provided a diagnostic NMR signal, which was observed as a broad singlet (δ 3.74 ppm) in the .sup.1H NMR spectrum; furthermore this peak integrated in a 3:2 ratio, when compared with the olefinic resonances at δ 5.41 ppm. In the case of M1, a crude reaction mixture from hydroaminoalkylation was found to be amenable to ROMP without purification by column chromatography, however the resulting material could, like P2 and P4, only be characterized by NMR and IR spectroscopy.
(178) Table 2 provides a summary of the exemplary polymers synthesized.
(179) TABLE-US-00002 TABLE 2 Overview of polymers synthesized. Compound ID IUPAC Name Chemical Structure P1 Poly(N-(oct-4-en-1- ylmethyl)aniline)
4.4 Hydrogenation
(180) Hydrogenative reduction of the polymer backbone of polymer P1 was targeted in order to obtain a saturated polymer analogous to polyethylene. The reduction could be realized using tosyl hydrazine as a hydrogen source that selectively reduced the C═C double bond of polymer P1. Due to the pendant secondary amine, a basic work-up of the polymer was required.
(181) Poly(N-(cyclooct-4-an-1-ylmethyl)aniline) (polymer “P1H”). P1 (480 mg, 2 mmol alkene) and p-toluenesulfonyl hydrazide (1.5 g, 8 mmol) in xylene (15 mL), along with a few mgs of 2,4,6-tri-tert-butyl phenol added as a radical sponge, were added to a 100 mL reaction vessel equipped with a Teflon capped-valve and side-arm and a Teflon-coated stir bar. The resulting heterogeneous mixture was filled with N.sub.2, freeze-pump-thawed three times, then back-filled with N.sub.2. The vessel was sealed and heated to 130° C. in an oil-bath for a minimum of 8 hours. After the duration of the reaction, a pale-yellow, clear solution was obtained. The vessel was opened and the mixture transferred to a separatory funnel, using ethyl acetate (50 mL) to quantitatively transfer. The organic layer was washed three times with 3 M NaOH, then once with brine, then reduced to 3 mL via rotary evaporation under reduced pressure. This residue was then added drop-wise to a large excess of vortexing methanol (−35° C., 250 mL) to afford the product as an off-white, gummy solid. After three excessive precipitations, 0.350 g of material was obtained (73.0%). .sup.1H NMR (300 MHz, CDCl.sub.3,
(182) Table 3 provides a summary of the exemplary hydrogenated polymers that were synthesized.
(183) TABLE-US-00003 TABLE 3 Overview of example compounds. Compound ID IUPAC Name Chemical Structure P1H Poly(N-(oct-4-an-1- ylmethyl)aniline)
(184) The secondary aryl amine and its substituents may be varied to tune hydrogen bonding interactions which may result in polymers displaying various physical properties, e.g. a liquid, gel-like, soft, or solid structure
Example 2: NMR Polymerization Study
(185) The polymerization of M1 was monitored by NMR spectroscopy. To a sealed NMR tube was added the Grubbs initiator, 100 equivalents of M1 and ca. 1 mL deuterated chloroform. After 10 min, approximately 35% of the monomer had been consumed; after 30 minutes the reaction had exceeded 95% completion. In contrast to other amine-functionalized monomers which are incompatible with Grubbs initiators, the rapid conversion of M1 shows that aryl substituted secondary amines are amenable to ROMP. Notably, throughout the polymerization, the signal assigned to the benzylidene Ru═CHPh proton at 19.2 ppm remained present in the spectrum (Figure X), wherein this observation may suggest incomplete initiation of the catalyst and rates of propagation that are greater than rates of catalyst initiation.
(186) To probe whether the chain termination took place upon reaction completion, an aliquot of ca. 25 equivalents of M2 was added long after monomer M1 had been fully consumed (12 hours). Upon addition of M2, rapid polymerization took place and no signals consistent with the internal alkene of M2 was observed after 30 minutes, while the overlapping alkene peaks of P1 and P2 suggest that polymerization is not self-terminating and the addition of a quenching reagent is required to complete the reaction. Furthermore, the .sup.19F NMR spectrum showed a single broad singlet consistent with ring-opened M2 polymeric material, corroborating the evidence present in the .sup.1H NMR spectrum.
4.4 Molecular Weight and Dispersity
(187) Polymers that possessed solubility in tetrahydrafuran (THF) were subjected to analysis using gel-permeation chromatography (GPC) to probe polymer molecular weight and dispersity (Table 2). Experimental molecular weights did not correlate exactly to the predicted by monomer-to-initiator ratios (M.sub.n,theo=[M]/[I]), while dispersity (Ð) values from 1.1 to 1.6 suggested that polymerization proceeded with only moderate control. As discussed previously, reaction monitoring suggested that rates of propagation were fast relative to initiation, resulting in larger than expected molecular weight and increased polymer dispersity. Notably, not all isolated polymers possessed solubility in THF for GPC analysis; for example, P4, with its hydrogen bonding methoxy substituent, could be characterized in chloroform by NMR spectroscopy but was not completely soluble in THF or chloroform. This observation may indicate that the formation of extensive hydrogen-bonding networks may result in lower solubility of the polymer, due to increased inter- and intra-molecular forces. P2 also showed this lack of solubility, presumably due to the strong H-bond accepting potential of the fluorine substituent.
(188) TABLE-US-00004 TABLE 2 Experimental and theoretical molecular weight (M.sub.n). [Ru]/ Theo. M.sub.n/ Exp. M.sub.n.sup.a/ Entry Polymer mol % g .Math. mol.sup.−1 g .Math. mol.sup.−1 .sup.a 2 P1 0.5 43,000 82,970 1.32 3 P1 1 21,500 18,100 1.40 5 P2 1 23,400 — — 6 P3 1 29,600 35,080 1.65 7 P4 1 24,700 — — .sup.aDetermined by Gel-permeation chromatography (GPC)
4.5 Thermal Stability
(189) Thermal stabilities (weight losses) of the polymers were determined by employing dynamic TGA experiments. Each sample was pre-heated at 105° C. for 5 min then heated from 30° C. to 600° C. at a heating rate of 10° C./min under nitrogen and oxygen.
(190) An average of three independent measurements was made. There was no difference in TGA curves for samples tested under nitrogen or oxygen atmosphere, indicating good thermo-oxidative stability.
(191) The derivative TGA, or DTG curves were useful for determination of the overlapping mass loss events, identification of minor mass loss steps, and finding the maxima of weight loss processes, wherein every peak in the TG curves may be an isolated event that may indicate the maximum rate of mass loss. Referring to
(192) TABLE-US-00005 TABLE 4 Thermal characterization by differential scanning calorimetry and thermogravimetric analysis. Polymers T.sub.g (° C.) T.sub.5% (° C.) P(cyclooctene) — 415 P1 −13.7 275 P2 −10.4 280 P3 −2.0 255 P4 −4.7 287 P1H −16.8 400
4.6 Rheology
(193) Representative master curves of shifted storage and loss moduli and complex viscosity of various amine derivatives of poly(cyclooctene) as a function of shifted angular frequency are depicted in
(194) TABLE-US-00006 TABLE 5A Rheological behaviors of polymer P1. Configuration Notes: Concentration Source: RI Flow Rate: 0.500 mL/min Light Scattering Instrument: miniDAWN TREOS Cell Type: Fused Silica Wavelength: 659.4 nm Calibration Constant: 4.8798 × 10.sup.−5 1/(V cm) RI Instrument: Optilab rEX Viscometer: ViscoStar Dilution Factor: 0.4972 Solvent: thf Temperature Correction Enabled: no Refractive Index: 1.402 Processing Collection Time: Tuesday Jun. 20, 2017 12:35:00 PM Pacific Daylight Time Processing Time: Wednesday Jun. 21, 2017 11:02:17 AM Pacific Daylight Time Peak settings: Peak Name Peak 1 Peak Limits (min) 10.360-18.692 Light Scattering Model Zimm Fit Degree 1 dn/dc (mL/g) 0.1068 A2 (mol mL/g.sup.2) 0.000 UV Ext. Coef. (mL/(mg cm)) 0.000 Viscometry Model Huggins Huggins Equation Parameter 0 Kraemers Equation Parameter 0 Molar Mass & Radius from LS: Enabled Detectors: 1 2 3 Results Fitting Procedure: Fit Extra- Data Model Degree R.sup.2 polation Molar Mass None n/a n/a none Rms Radius None n/a n/a none Mean Square Radius None n/a n/a none Hydrodynamic Radius (Q) None n/a n/a none Results Peak Results Peak 1 Hydrodynamic radius (v) moments (nm) Rh(v)n 2.604 (±2.059%) Rh(v)w 3.097 (±1.947%) Rh(v)z 3.709 (±2.067%) Masses Calculated Mass (μg) 243.98 Mass Recovery (%) 100.0 Mass Fraction (%) 100.0 Molar mass moments (g/mol) Mn 1.810 × 10.sup.4 (±4.998%) Mp 2.505 × 10.sup.4 (±4.301%) Mv 2.355 × 10.sup.4 (±0.234%) Mw 2.527 × 10.sup.4 (±4.388%) Mz 3.526 × 10.sup.4 (±9.764%) Polydispersity Mw/Mn 1.397 (±6.651%) Mz/Mn 1.949 (±10.969%) rms radius moments (nm) Rn 2.7 (±2275.8%) Rw 7.6 (±273.0%) Rz 10.1 (±148.5%) Intrinsic viscosity moments (mL/g) [η]n 6.663 (±3.679%) [η]w 8.11 (±3.49%) [η]z 9.881 (±4.059%) Mark-Houwink-Sakurada a: 0.595 (±0.459%) Mark-Houwink-Sakurada K: 2.041 × 10.sup.−2 (±2.803%) mL/g
(195) TABLE-US-00007 TABLE 5B Rheological behaviors of polymer P1H prior to hydrogentation. Configuration Notes: Concentration Source: RI Flow Rate: 0.500 mL/min Light Scattering Instrument: miniDAWN TREOS Cell Type: Fused Silica Wavelength: 659.4 nm Calibration Constant: 4.8798 × 10.sup.−5 1/(V cm) RI Instrument: Optilab rEX Viscometer: ViscoStar Dilution Factor: 0.4972 Solvent: thf Temperature Correction Enabled: no Refractive Index: 1.402 Processing Collection Time: Thursday Jul. 27, 2017 09:21:33 AM Pacific Daylight Time Processing Time: Thursday Aug. 10, 2017 11:29:41 AM Pacific Daylight Time Peak settings: Peak Name Peak 1 Peak Limits (min) 10.273-15.431 Light Scattering Model Zimm Fit Degree 1 dn/dc (mL/g) 0.1217 A2 (mol mL/g.sup.2) 0.000 UV Ext. Coef. (mL/(mg cm)) 0.000 Viscometry Model Huggins Huggins Equation Parameter 0 Kraemers Equation Parameter 0 Molar Mass & Radius from LS: Enabled Detectors: 1 2 3 Results Fitting Procedure: Fit Extra- Data Model Degree R.sup.2 polation Molar Mass None n/a n/a none Rms Radius None n/a n/a none Mean Square Radius None n/a n/a none Hydrodynamic Radius (Q) None n/a n/a none Results Pe Peak Results Peak 1 Hydrodynamic radius (v) moments (nm) Rh(v)n 6.465 (±0.962%) Rh(v)w 7.437 (±0.918%) Rh(v)z 9.278 (±1.010%) Masses Calculated Mass (μg) 147.97 Mass Recovery (%) 100.0 Mass Fraction (%) 100.0 Molar mass moments (g/mol) Mn 7.357 × 10.sup.4 (±2.562%) Mp 9.930 × 10.sup.4 (±2.425%) Mv 9.110 × 10.sup.4 (±0.177/0) Mw 9.831 × 10.sup.4 (±2.461%) Mz 1.587 × 10.sup.5 (±5.461%) Polydispersity Mw/Mn 1.336 (±3.553%) Mz/Mn 2.156 (±6.032%) rms radius moments (nm) Rn 21.4 (±21.5%) Rw 21.7 (±20.7%) Rz 22.3 (±19.2%) Intrinsic viscosity moments (mL/g) [η]n 24.537 (±1.116%) [η]w 28.97 (±0.94%) [η]z 37.624 (±1.610%) Mark-Houwink-Sakurada a: 0.587 (±0.163%) Mark-Houwink-Sakurada K: 3.619 × 10.sup.−2 (±1.111%) mL/g
(196) TABLE-US-00008 TABLE 5C Rheological behaviors of polymer P1H. Configuration Notes: Concentration Source: RI Flow Rate: 0.500 mL/min Light Scattering Instrument: miniDAWN TREOS Cell Type: Fused Silica Wavelength: 659.4 nm Calibration Constant: 4.8798 × 10.sup.−5 1/(V cm) RI Instrument: Optilab rEX Viscometer: ViscoStar Dilution Factor: 0.4972 Solvent: thf Temperature Correction Enabled: no Refractive Index: 1.402 Processing Collection Time: Wednesday Aug. 16, 2017 01:48:03 PM Pacific Daylight Time Processing Time: Thursday Aug. 17, 2017 12:32:27 PM Pacific Daylight Time Peak settings: Peak Name Peak 1 Peak Limits (min) 9.078-17.166 Light Scattering Model Zimm Fit Degree 1 dn/dc (mL/g) 0.1182 A2 (mol mL/g.sup.2) 0.000 UV Ext. Coef. (mL/(mg cm)) 0.000 Viscometry Model Huggins Huggins Equation Parameter 0 Kraemers Equation Parameter 0 Molar Mass & Radius from LS: Enabled Detectors: 1 2 3 Results Fitting Procedure: Fit Extra- Data Model Degree R.sup.2 polation Molar Mass None n/a n/a none Rms Radius None n/a n/a none Mean Square Radius None n/a n/a none Hydrodynamic Radius (Q) None n/a n/a none Results Peak Results Peak 1 Hydrodynamic radius (v) moments (nm) Rh(v)n 6.165 (±1.466%) Rh(v)w 6.804 (±1.444%) Rh(v)z 7.984 (±1.516%) Masses Calculated Mass (μg) 159.99 Mass Recovery (%) 100.0 Mass Fraction (%) 100.0 Molar mass moments (g/mol) Mn 7.123 × 10.sup.4 (±3.741%) Mp 8.224 × 10.sup.4 (±3.418%) Mv 8.257 × 10.sup.4 (±0.218%) Mw 8.710 × 10.sup.4 (±3.581%) Mz 1.201 × 10.sup.5 (±8.008%) Polydispersity Mw/Mn 1.223 (±5.179%) Mz/Mn 1.686 (±8.839%) rms radius moments (nm) Rn 23.5 (±23.9%) Rw 23.2 (±23.9%) Rz 23.1 (±23.6%) Intrinsic viscosity moments (mL/g) [η]n 21.831 (±1.685%) [η]w 24.71 (±1.68%) [η]z 29.566 (±2.407%) Mark-Houwink-Sakurada a: 0.601 (±0.222%) Mark-Houwink-Sakurada K: 2.989 × 10.sup.−2 (±1.536%) mL/g
(197) TABLE-US-00009 TABLE 5D Rheological behaviors of polymer P3. Configuration Notes: Concentration Source: RI Flow Rate: 0.500 mL/min Light Scattering Instrument: miniDAWN TREOS Cell Type: Fused Silica Wavelength: 659.4 nm Calibration Constant: 4.8798 × 10.sup.−5 1/(V cm) RI Instrument: Optilab rEX Viscometer: ViscoStar Dilution Factor: 0.4972 Solvent: thf Temperature Correction Enabled: no Refractive Index: 1.402 Processing Collection Time: Thursday Jul. 27, 2017 12:04:40 PM Pacific Daylight Time Processing Time: Thursday Aug. 10, 2017 11:22:31 AM Pacific Daylight Time Peak settings: Peak Name Peak 1 Peak Limits (min) 8.699-17.441 Light Scattering Model Zimm Fit Degree 1 dn/dc (mL/g) 0.1179 A2 (mol mL/g.sup.2) 0.000 UV Ext. Coef. (mL/(mg cm)) 0.000 Viscometry Model Huggins Huggins Equation Parameter 0 Kraemers Equation Parameter 0 Molar Mass & Radius from LS: Enabled Detectors: 1 2 3 Results Fitting Procedure: Fit Extra- Data Model Degree R.sup.2 polation Molar Mass None n/a n/a none Rms Radius None n/a n/a none Mean Square Radius None n/a n/a none Hydrodynamic Radius (Q) None n/a n/a none Results Pe Peak Results Peak 1 Hydrodynamic radius (v) moments (nm) Rh(v)n 3.615 (±2.518%) Rh(v)w 4.737 (±1.844%) Rh(v)z 6.387 (±1.847%) Masses Calculated Mass (μg) 133.00 Mass Recovery (%) 100.0 Mass Fraction (%) 100.0 Molar mass moments (g/mol) Mn 3.508 × 10.sup.4 (±2.050%) Mp 5.788 × 10.sup.4 (±2.766%) Mv 5.136 × 10.sup.4 (±0.167/0) Mw 5.802 × 10.sup.4 (±2.577%) Mz 1.007 × 10.sup.5 (±6.010%) Polydispersity Mw/Mn 1.654 (±3.293%) Mz/Mn 2.870 (±6.350%) rms radius moments (nm) Rn n/a Rw 10.5 (±71.9%) Rz 15.7 (±35.9%) Intrinsic viscosity moments (mL/g) [η]n 9.733 (±5.087%) [η]w 13.61 (±3.65%) [η]z 18.507 (±4.394%) Mark-Houwink-Sakurada a: 0.580 (±0.380%) Mark-Houwink-Sakurada K: 2.753 × 10.sup.−2 (±2.463%) mL/g
4.7 Self-Healing Properties
(198) Referring to
4.8 Copolymers
(199) 4.8.1 Copolymers with Cyclooctene
(200) In an attempt to explore the extent to which the advantageous properties of these novel polymers could be retained with lower incorporations of amine in the polymer, the amine incorporation in the final polymer was reduced by adding excess equivalents of cyclooctene to the ROMP reaction. The ultimate goal is to maintain the desirable properties imparted by the amine functional group while lowering its incorporation in less expensive, less functionalized polyolefins.
(201) Synthesis of polymer with reduced amine incorporation was conducted according to the following scheme.
(202) ##STR00049##
(203) P(P1-co-cyclooctene) General preparation for a 1:1 by mol copolymer was prepared as follows: To a 20 mL scintillation vial was added the first monomer, eg. cyclooctene (51 mg, 0.4 mmol) and a solution of G2 (3.7 mg, 0.004 mmol) in THF (1 mL) with a stir bar. After reacting the first monomer at room temperature for the time required (eg. 4 hrs for cyclooctene), the second monomer, eg. M1 (100 mg, 0.4 mmol. 1:1 mol ratio with cyclooctene). After time required to react second monomer, the entire reaction was quenched and polymer isolated using standard practice with addition of ethyl vinyl ether and precipitation into methanol. .sup.1H NMR (300 MHz, CDCl.sub.3): δ 7.19 (m, 2H, 2×ArH), δ 6.71 (br s, 3H, 3×ArH), δ 5.40 (m, 4H, RHC═CHR), δ 3.03 (d, 2H, CH.sub.2), δ 2.00 (m, 8H, CH.sub.2), δ 1.68 (br s, 1H, CH), δ 1.49-1.26 (m, 14H, CH.sub.2). The results of the synthesis are further reported in Table 6 below.
(204) TABLE-US-00010 TABLE 6 First Second monomer monomer Characterization cyclooctene M1 M.sub.n, calc = 19,019; Ð = 1.48*. .sup.1H NMR: 59/41 M1:M2 cyclooctene M1 M.sub.n, calc = 36,951; Ð = 1.07*. .sup.1H NMR: 57/43 M1:M2 M.sub.n, calc determined using molecular weight of quenched aliquot of P1 then relating MW of P2 by using integrations in .sup.1H NMR spectrum.
(205) 4.8.2 Copolymers with Arylamine Substituted Norbornene Monomer Units
(206) In contrast to the polymers disclosed and prepared herein, polymers formed from arylamine substituted norbornene monomers do not show self-healing behaviour. It was of interest to combine these monomers to explore whether this behavior could be tuned and allow for the preparation of materials with variable physical properties Co-polymers of the amine-functionalized cycloalkene monomers disclosed above and several arylamine substituted norbornene monomers including:
(207) ##STR00050##
(208) Monomers ACN-1 and ACN-4 can be prepared as disclosed by Perry et al. (Macromolecules, 49: 4423 to 4430).
(209) A simultaneous addition of monomers was employed in the attempted formation of copolymers
(210) ##STR00051##
(211) A series of different combinations of monomers with varying para R/R′ substituents were co-polymerized via ROMP (50 equivalents of each monomer). Copolymers were prepared as in homopolymers using various stoichiometric amounts of the different monomers to give theoretical ratio in polymer product. A typical procedure is as follows:
(212) ##STR00052##
(213) To a 20 mL scintillation vial was added ACN-1 (50 mg, 0.25 mmol) and polymer P2 (58 mg, 0.25 mmol) with ca. 1 mL CH.sub.2Cl.sub.2. To this solution was added a solution of Grubbs Catalyst™ 2nd Generation (“G2”; 4.2 mg, 0.005 mmol) in ca. 1 mL CH.sub.2Cl.sub.2. The reaction was stirred for 20 h at room temperature, during which the solution slowly goes brown-green from the initial amber color. The polymer was isolated using standard practice with addition of ethyl vinyl ether and precipitation into methanol; yields are quantitative with losses due to collection from precipitation. .sup.1H NMR (300 MHz, CDCl.sub.3): δ 7.16 (s, 2H, 2×ArH), δ 6.87 (m, 2H, 2×ArH), δ 6.75 (m, 3H, 3 ArH), δ 6.55 (br s, 2H, 2×ArH), δ 5.39-5.27 (m, 4H, 2×RHC═CHR), δ 3.05-2.97 (d, 4H, CH.sub.2), δ 2.90 (s, 1H, CH), δ 2.53 (s, 1H, CH), δ 2.00-1.95 (m, 6H, CH.sub.2), δ 1.65-1.63 (br s, 3H), δ 1.36 (br s, 6H, CH.sub.2), δ 1.19 (s, 1H, CH).
(214) Isolation of quenched reaction solutions by precipitation gave a material with physical properties that are intermediate to the respective homopolymers. Where homopolymers made from arylamine substituted norbornene monomers are stiff threads, and homopolymers as disclosed herein are sticky and tough gums, the copolymers aggregate and are tacky as in the latter, however with more pronounced stiffness. By .sup.1H NMR spectroscopy, it was found that the resultant polymers had higher incorporations of the given ACN (52-74%). ACN-1 (R═H) and ACC-2 (R′ ═F) was chosen as a model system as both monomers were evenly incorporated (52:48 ACN:ACC). To ensure that a copolymer was formed, rather than two homopolymers, GPC analysis was performed on this sample; one peak was observed with reasonable agreement to the theoretical value (M.sub.n, exp=18,130 g.Math.mol.sup.−1,Ð=1.61, M.sub.n, theo.=21,630 g.Math.mol.sup.−1).
(215) To explore whether the thermal properties can be tuned based on the relative incorporation of monomers, three different ratios of the polymer P(ACN-1-co-P2) model system were prepared. The experimental ratios determined by .sup.1H NMR spectroscopy are indicated in Table 7. The glass transition temperatures as determined by DSC are shown in Table 7 and
(216) TABLE-US-00011 TABLE 7 Ratios of monomer in co-polymer. % ACN theo. % ACN exp..sup.a T.sub.g.sup.b/° C. 0.00 0.00 −10.4 0.25 0.28 8.55 0.50 0.52 17.3 0.75 0.81 37.6 1.00 1.00 58.4 .sup.aCalculated by .sup.1H NMR spectroscopy .sup.bDetermined by DSC
(217) The effects of these varied ratios on viscoelasticity was examined. Referring to
(218) Qualitative healing tests were performed to explore the effect of varying the glass transition temperature (T.sub.g). It was hypothesized that all samples that had a glass transition below room temperature would demonstrate self-healing. Of the three copolymers, only the sample with 3:1 M2:ACN-1 ratio (T.sub.g=8.6° C.) demonstrated healing within 24 hours. The sample with 1:1 M2:ACN-1 (T.sub.g=17.3° C.) did not demonstrate healing at the ambient conditions. These results suggest that tuning the thermal behavior may allow tuning of healing time depending on the needs of the material.
(219) While specific embodiments of the invention have been described and illustrated, such embodiments should be considered illustrative of the invention only and not as limiting the invention as construed in accordance with the accompanying claims. Many adaptations and modifications may be made within the scope of the invention in accordance with the common general knowledge of those skilled in this art. Such modifications include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way.