Polystyrene sulfonate analogs and methods
10640587 ยท 2020-05-05
Assignee
Inventors
Cpc classification
C08G61/08
CHEMISTRY; METALLURGY
C08G2261/418
CHEMISTRY; METALLURGY
International classification
Abstract
Provided are polystyrene sulfonate analogs and methods of making polystyrene sulfonate analogs. The polystyrene sulfonate analogs may be formed by a ring opening metathesis polymerization (ROMP). The ROMP may provide analogs having a precise periodicity. The polystyrene sulfonate analogs may have a relatively low glass transition temperature.
Claims
1. A polymer comprising repeat units according to Formula (B): ##STR00011## wherein R.sub.1-R.sub.10 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C.sub.1-C.sub.10 hydrocarbyl, at least one of R.sub.1-R.sub.5 is sulfonate or sulfonic acid, n and m independently are 1 to 10,000, and wherein at least one of the repeat units comprising R.sub.1-R.sub.5 is covalently bonded to at least one of the repeat units comprising R.sub.6-R.sub.10.
2. The polymer of claim 1, wherein the polymer has a degree of sulfonation of about 1% to about 125%.
3. The polymer of claim 1, wherein the polymer has a degree of sulfonation of about 80% to about 120%.
4. The polymer of claim 1, wherein at least one of R.sub.6-R.sub.10 is sulfonate or sulfonic acid, and the polymer has a degree of sulfonation of about 100% to about 120%.
5. The polymer of claim 1, wherein the polymer has a glass transition temperature (T.sub.g) of about 5 C. to about 145 C.
6. The polymer of claim 1, wherein the polymer has a glass transition temperature (T.sub.g) of about 10 C. to about 30 C.
7. The polymer of claim 1, wherein the polymer is at least partially cross-linked.
8. A polymer consisting of repeat units according to Formula (A): ##STR00012## wherein, independently for each of the repeat units of Formula (A), R.sub.1-R.sub.5 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C.sub.1-C.sub.10 hydrocarbyl, at least one of R.sub.1-R.sub.5 of at least one of the repeat units of Formula (A) is sulfonate or sulfonic acid, and n is 200 to 10,000.
9. The polymer of claim 8, wherein the polymer has a glass transition temperature (T.sub.g) of about 5 C. to about 145 C.
10. The polymer of claim 8, wherein the polymer has a glass transition temperature (T.sub.g) of about 10 C. to about 30 C.
11. The polymer of claim 8, wherein R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is sulfonate or sulfonic acid.
12. The polymer of claim 8, wherein the polymer is at least partially cross-linked.
13. A method of making a polymer, the method comprising: contacting a compound of formula (I) with a catalyst to form an unsaturated polymer by ring opening metathesis polymerization ##STR00013## wherein R.sub.11-R.sub.15 are independently selected from hydrogen or a monovalent C.sub.1-C.sub.10 hydrocarbyl; contacting the unsaturated polymer with a hydrogenation agent to form a saturated polymer; contacting the saturated polymer with a sulfonating agent to form a saturated polymer substituted with sulfonic acid; and optionally deprotonating the saturated polymer substituted with sulfonic acid to form a saturated sulfonated polymer.
14. The method of claim 13, wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a glass transition temperature (T.sub.g) of about 5 C. to about 145 C.
15. The method of claim 13, wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a glass transition temperature (T.sub.g) of about 10 C. to about 30 C.
16. The method of claim 13, wherein, prior to the contacting of the saturated polymer with the sulfonating agent, the molar mass of the saturated polymer is about 45 kg/mol to about 160 kg/mol.
17. The method of claim 13, wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a degree of sulfonation of about 1% to about 125%.
18. The method of claim 13, wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a degree of sulfonation of about 80% to about 120%.
19. The method of claim 13, further comprising at least partially cross-linking the unsaturated polymer prior to the contacting of the unsaturated polymer with the hydrogenation agent.
Description
BRIEF DESCRIPTION OF THE FIGURES
(1)
(2)
(3)
(4)
(5)
DETAILED DESCRIPTION
(6) Other objects, features, and advantages of the invention will be apparent from the following detailed description, drawings, and claims. Unless otherwise defined, all technical and scientific terms and abbreviations used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and compositions similar or equivalent to those described herein can be used in the practice of the present invention, suitable methods and compositions are described without intending that any such methods and compositions limit the invention herein.
(7) Polymers
(8) In embodiments, the polymers herein include a repeat unit having the following structure:
(9) ##STR00004##
wherein R.sub.1-R.sub.5 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C.sub.1-C.sub.10 hydrocarbyl, at least one of R.sub.1-R.sub.5 is sulfonate or sulfonic acid, and n is 1 to 10,000. In one embodiment, R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is sulfonate or sulfonic acid. In another embodiment, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.1 is sulfonate or sulfonic acid. In a further embodiments, R.sub.1, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.2 is sulfonate or sulfonic acid. In an additional embodiment, R.sub.1, R.sub.2, R.sub.3, and R.sub.5 are hydrogen, and R.sub.4 is sulfonate or sulfonic acid. In a still further embodiment, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen, and R.sub.5 is sulfonate or sulfonic acid.
(10) In some embodiments, n of Formula (A) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.
(11) In embodiments, the polymers herein comprise the repeat units of Formula (B):
(12) ##STR00005##
wherein R.sub.1-R.sub.10 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C.sub.1-C.sub.10 hydrocarbyl, at least one of R.sub.1-R.sub.5 is sulfonate or sulfonic acid, and n and m independently are 1 to 10,000.
(13) In some embodiments, at least one of R.sub.1-R.sub.5 may differ from at least one of R.sub.6-R.sub.10 in the polymers of Formula (B). Therefore, the term polymer as used herein, refers to and includes both polymers and copolymers.
(14) The degree of sulfonation of the polymers provided herein may be about 1% to about 150%, about 1% to about 125%, about 1 to about 100%, about 75% to about 125%, or about 80% to about 120%. In some embodiments, at least one of R.sub.6-R.sub.10 is sulfonate or sulfonic acid, and the degree of sulfonation is at least 100%, about 100% to about 150%, about 100% to about 125%, or about 100% to about 110%.
(15) In some embodiments, the sum of m and n of Formula (B) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.
(16) The degree of sulfonation, which is provided as a percentage herein, generally indicates the average number of sulfonate or sulfonic acid substituents per phenyl pendant group of the polymers provided herein. For example, a degree of sulfonation of 100% indicates an average of one sulfonate or sulfonic acid substituent per phenyl pendant group. Degrees of sulfonation less than 100% indicate an average of less than one sulfonate or sulfonic acid substituent per phenyl pendant group, and degrees of sulfonation greater than 100% indicate an average of more than one sulfonate or sulfonic acid substituent per phenyl pendant group, thereby indicating that a least a portion of the phenyl pendant groups should be substituted with more than one sulfonate or sulfonic acid substituent. For example, a degree of sulfonation of 80% indicates that an average of 80 out of every 100 phenyl pendant groups are substituted with one sulfonate or sulfonic acid substituent.
(17) Generally, the polymers of Formula (B) herein may include any ratio of min to n in order to achieve a desired degree of sulfonation. For example, R.sub.3 may be a sulfonate; R.sub.1, R.sub.2, and R.sub.4-R.sub.10 may be hydrogen; and the ratio of n:m may be 80:20, thereby imparting the polymer with a degree of sulfonation of 80%.
(18) The polymers may include any end groups known in the art, including, but not limited to end groups derived from ethyl vinyl ether, or by end groups derived from telechelic chain transfer agents.
(19) The polymers herein may be cross-linked. The cross-linking may be achieved via olefins in a polymer's backbone, such as those that are present in the intermediate polypentenamer described herein (see, e.g., Scheme 1). Therefore, as used herein, the symbol may represent one bond in polymers that are not cross-linked, or two bonds in polymers that are cross-linked. For example, when the polymers are not cross-linked, the symbol
may represent one bond between the carbon atom of the monomer and [1] an adjacent monomer of the polymer chain, or [2] an end group; and when the polymers are cross-linked, the symbol
may represent two bonds, such as a first bond between the carbon atom of the monomer and [1] an adjacent monomer of the polymer chain or [2] an end group, and a second bond between the carbon atom of the monomer and [1] a non-adjacent monomer of the polymer chain or [2] a monomer of a different polymer chain. The terms monomer and repeat unit are used interchangeably herein.
(20) The glass transition temperature (T.sub.g) of the polymers provided herein may be about 5 C. to about 145 C., about 5 C. to about 125 C., about 5 C. to about 100 C., about 5 C. to about 75 C., about 5 C. to about 50 C., about 5 C. to about 40 C., about 10 C. to about 30 C., about 15 C. to about 20 C., or about 17 C.
(21) The polymers provided herein may be employed in block copolymers. For example, the products provided herein may be employed in block copolymers through utilization of chain transfer agents which may install functionalities for sequential growth of alternative polymer segments.
(22) Methods of Making Polymers
(23) Methods of making polymers, such as those of Formula (A) and Formula (B), respectively, are provided herein.
(24) In embodiments, the methods provided herein include contacting a compound of formula (I) with a catalyst to facilitate ring-opening metathesis polymerization (ROMP) to form an unsaturated polymer
(25) ##STR00006##
wherein R.sub.11-R.sub.15 are independently selected from hydrogen or a C.sub.1-C.sub.10 hydrocarbyl. In some embodiments, R.sub.11-R.sub.15 are hydrogen. The compounds of Formula (I) may be copolymerized with other cyclopentene-based derivatives, including one or more analogues of Formula (I) having different substituents at the positions of R.sub.11-R.sub.15.
(26) In some embodiments, the catalyst to facilitate ROMP includes ruthenium, molybdenum, tunsgsten, or a combination thereof. For example, the catalyst may be a Schrock-type catalyst that includes molybdenum and/or tungsten.
(27) In some embodiments, the contacting of a compound of formula (I) with a catalyst to facilitate ROMP occurs in the presence of toluene, tetrahydrofuran (THF), dichloromethane (DCM), or a combination thereof.
(28) In some embodiments, the contacting of a compound of formula (I) with a catalyst to facilitate ROMP occurs at a temperature of about 20 C. to about 50 C.
(29) In some embodiments, the unsaturated polymer produced by the ROMP has the following structure:
(30) ##STR00007##
wherein n is 1 to 10,000. In some embodiments, n of Formula (II) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700. The unsaturated bonds of an unsaturated polymer may have a cis or trans configuration. Any ratio (e.g., from 0:100 to 100:0) of cis to trans double bonds may be present in an unsaturated polymer. In some embodiments, an unsaturated polymer has a ratio of cis to trans double bonds of 10-30:70-90.
(31) In some embodiments, the methods provided herein include cross-linking the unsaturated polymer. The unsaturated polymer may be partially cross-linked. For example, a partially cross-linked unsaturated polymer may be one in which the number of unsaturated bonds is reduced by about 1% to about 50%, about 1% to about 25%, or about 1% to about 10% as a result of the cross-linking, which may be determined by any known techniques, such as the comparison of .sup.1H-NMR data collected before and after cross-linking (see, e.g.,
(32) The methods provided herein may include contacting an unsaturated polymer with a hydrogenation agent to form a saturated polymer. Generally, the hydrogenation agent may be any hydrogenation agent capable of saturating olefins, including hydrogenation agents capable of saturating olefins, but not aromatic moieties, such as a phenyl group. In some embodiments, the hydrogenation agent includes p-tosylhydrazide. The hydrogenation agent may partially or completely hydrogenate the unsaturated bonds. In some embodiments, the hydrogenation agent hydrogenates at least 99% of the unsaturated bonds.
(33) In embodiments, prior to the contacting of a saturated polymer with a sulfonating agent, the molar mass of a saturated polymer, which may or may not be cross-linked, is about 1 kg/mol to about 300 kg/mol, about 1 kg/mol to about 200 kg/mol, about 10 kg/mol to about 125 kg/mol, about 50 kg/mol to about 100 kg/mol, about 75 kg/mol to about 80 kg/mol. In embodiments, prior to the contacting of a saturated polymer with a sulfonating agent, the molar mass of a saturated polymer, which may or may not be cross-linked, is about 45,000 kg/mol to about 160,000 kg/mol. As used herein, the phrase molar mass refers to the number average molecular weight, unless noted otherwise.
(34) The methods provided herein may include contacting a saturated polymer with a sulfonating agent to substitute a saturated polymer with a sulfonic acid. The sulfonic acid may be substituted on a phenyl pendant group, for example, at one or more of positions R.sub.11-R.sub.15 of Formulas (I) and (II). Any known sulfonating agent may be used. In embodiments, the sulfonating agent includes H.sub.2SO.sub.4. The sulfonating agent also may include one or more additives, such as FeSO.sub.4, that may aid in sulfonation.
(35) The methods provided herein may include deprotonating a sulfonic acid substituent to form a saturated sulfonated polymer. The deprotonating of a sulfonic acid substituent may include contacting a sulfonic acid substituent with a cationic metal salt. For example, the deprotonating may be achieved with a countercation selected from Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, or a combination thereof. In some embodiments, deprotonating the sulfonic acid to form a saturated sulfonated polymer includes contacting the saturated polymer substituted with sulfonic acid with a metal hydroxide base, including, but not limited to, NaOH, KOH, LiOH, or a combination thereof. It is believed that the deprotonation of the sulfonic acid groups can ionize the polymer with various metal cations.
(36) In embodiments, the substituted saturated polymer or the saturated sulfonated polymer, each of which may or may not be cross-linked, has a degree of sulfonation of about 1% to about 125%, about 75% to about 125%, or about 80% to about 120%; and a glass transition temperature of about 5 C. to about 40 C., about 10 C. to about 30 C., about 15 C. to about 20 C., or about 17 C.
(37) The phrases C.sub.1-C.sub.10 hydrocarbyl and the like, as used herein, generally refer to aliphatic, aryl, or arylalkyl groups containing 1 to 10 carbon atoms. Examples of aliphatic groups, in each instance, include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having 1 to 10 carbon atoms, 2 to 8 carbon atoms, 4 to 6 carbon atoms, etc. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl and dodecyl. Cycloalkyl moieties may be monocyclic or multicyclic, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Additional examples of alkyl moieties have linear, branched and/or cyclic portions (e.g., 1-ethyl-4-methyl-cyclohexyl). Representative alkenyl moieties include vinyl, allyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl and 3-decenyl. Representative alkynyl moieties include acetylenyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonynyl, 2-nonynyl, 8-nonynyl, 1-decynyl, 2-decynyl and 9-decynyl. Examples of aryl or arylalkyl moieties include, but are not limited to, anthracenyl, azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenanthrenyl, phenyl, 1,2,3,4-tetrahydro-naphthalene, tolyl, xylyl, mesityl, benzyl, and the like, including any heteroatom substituted derivative thereof.
(38) Unless otherwise indicated, the term substituted, when used to describe a chemical structure or moiety, refers to a derivative of that structure or moiety wherein one or more of its hydrogen atoms is substituted with a chemical moiety or functional group such as alcohol, alkoxy, alkanoyloxy, alkoxycarbonyl, alkenyl, alkyl (e.g., methyl, ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (OC(O)alkyl), amide (C(O)NH-alkyl- or -alkylNHC(O)alkyl), tertiary amine (such as alkylamino, arylamino, arylalkylamino), aryl, aryloxy, azo, carbamoyl (NHC(O)O alkyl- or OC(O)NH-alkyl), carbamyl (e.g., CONH.sub.2, as well as CONH-alkyl, CONH-aryl, and CONH-arylalkyl), carboxyl, carboxylic acid, cyano, ester, ether (e.g., methoxy, ethoxy), halo, haloalkyl (e.g., CCl.sub.3, CF.sub.3, C(CF.sub.3).sub.3), heteroalkyl, isocyanate, isothiocyanate, nitrile, nitro, phosphodiester, sulfide, sulfonamido (e.g., SO.sub.2NH.sub.2), sulfone, sulfonyl (including alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl), sulfoxide, thiol (e.g., sulfhydryl, thioether) or urea (NHCONH-alkyl-).
(39) The terms a, an, and the are intended to include plural alternatives, e.g., at least one. For instance, the disclosure of a catalyst, a monomer, and the like, is meant to encompass one, or mixtures or combinations of more than one catalyst, monomer, and the like, unless otherwise specified.
(40) Various numerical ranges may be disclosed herein. When Applicant discloses or claims a range of any type, Applicant's intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. Moreover, all numerical end points of ranges disclosed herein are approximate. As a representative example, Applicant discloses, in one embodiment, that the glass transition temperature (T.sub.g) of the polymer is about 15 C. to about 20 C.. This range should be interpreted as encompassing values in a range of about 15 C. to about 20 C., and further encompasses about each of 16 C., 17 C., 18 C., and 19 C., including any ranges and sub-ranges between any of these values.
(41) The processes described herein may be carried out or performed in any suitable order as desired in various implementations. Additionally, in certain implementations, at least a portion of the processes may be carried out in parallel. Furthermore, in certain implementations, less than or more than the processes described may be performed.
(42) Many modifications and other implementations of the disclosure set forth herein will be apparent having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosure is not to be limited to the specific implementations disclosed and that modifications and other implementations are intended to be included within the scope of the appended claims.
EXAMPLES
(43) The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. Thus, other aspects of this invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.
(44) The following materials were used in the examples, unless noted otherwise. Allyltrimethylsilane (98%), benzaldehyde (>99.5%), basic alumina, butylated hydroxytoluene (99.0%), chloroform-d, ethyl vinyl ether (99.0%), calcium sulfate (99.5%), o-xylene (97%), p-toluenesulfonhydrazide (97%), phosphorous pentoxide (98.0%), Grubbs 1.sup.st generation catalyst (G1) (97.0%), Grubbs 3.sup.rd generation catalyst (G3) (97.0%), titanium tetrachloride (98.0%), toluene-d8, and tributylamine (98.5%) were purchased from Sigma-Aldrich and used as received.
(45) Dichloromethane (DCM) was purified by distillation over phosphorous pentoxide and purged with argon. Nitromethane was dried with calcium chloride and then distilled and purged with argon. Dry toluene and tetrahydrofuran (THF) were obtained from an SPS-4 solvent purification system. Grubbs 2.sup.nd generation catalyst (G2) and Hoveyda-Grubbs 2.sup.nd generation (HG2) catalyst were provided by Materia Inc. A dry ice/chloroform bath and hexane/liquid nitrogen bath were used for reaction cooling to 612 C. and 942 C., respectively.
(46) The following characterization methods were used in the examples, unless noted otherwise. .sup.1H and .sup.13C NMR experiments were performed on a Bruker 600 MHz and 150 MHz, NMR instrument, respectively, unless otherwise noted. VT-.sup.1H-NMR experiments were conducted on a Bruker 500 MHz instrument. .sup.1H-.sup.1H Correlation Spectroscopy (COSY) and Heteronuclear Multiple-Quantum Correlation (HMQC)-NMR were performed on a Bruker 600 MHz and 15 MHz instrument, respectively.
(47) Polymer molar mass and dispersities were determined on an Agilent-Wyatt combination triple detection size exclusion chromatography (SEC) instrument containing 3 successive Agilent PLgel Mixed C columns, an Agilent 1260 infinity series pump, degasser, autosampler, and thermostatted column chamber. The Wyatt triple detection unit hosted a miniDawn TREOS 3-angle light scattering detector, Optilab TrEX refractive index detector, and a Viscostar II differential viscometer.
(48) Molar mass and dispersities were determined by a 10-point universal calibration with narrow dispersity polystyrene standards varying from 580 to 7,500,000 Da. Differential scanning calorimetry (DSC) experiments were performed on a TA Instruments Model Q100. A heating rate of 10 C./minute under argon flow (40 mL/min) was used. Cooling was provided by an RCS cooler (Model No. RCS 90, refrigerated cooling system). Thermogravimetric analysis (TGA) was performed on a TA Instruments Model Q50.
(49) Infrared spectroscopy was performed on a PerkinElmer 100 FT-IR spectrometer with a diamond ATR accessory.
Example 1Synthesis of 4-phenyl-1,6-heptadiene
(50) A monomer precursor, 4-phenyl-1,6-heptadiene, was synthesized according to the following procedure. To a flame-dried round-bottom flask, a magnetic stir bar, anhydrous CH.sub.2Cl.sub.2 (300 mL) that was previously purged with argon, and MeNO.sub.2 (18 mL) that was previously purged with argon were added. The solution was kept under an argon blanket throughout.
(51) The solution was cooled to 61 C. with chloroform and dry ice. TiCl.sub.4 (13.32 mL, 121.5 mmol) and benzaldehyde (7.9616 g, 75 mmol) in CH.sub.2Cl.sub.2 (30 mL) were added sequentially. After 15 minutes of stirring, the mixture was cooled to 94 C. with hexanes and liquid nitrogen and allyltrimethylsilane (47.67 mL, 300 mmol, 4 eq.) in anhydrous CH.sub.2Cl.sub.2 (30 mL) was added over 10 minutes.
(52) The mixture was stirred at 91 C. for 3 hours and then warmed to 61 C. for 20 hours. The mixture was quenched with a saturated solution of NH.sub.4Cl. The product was extracted and the aqueous layer was washed twice with DCM. The organic layer was then washed with a saturated NaCl solution. The organic layer was collected and dried over CaSO.sub.4 prior to concentrating via rotary evaporation. The crude product (yellow oil) was purified by flash chromatography on silica gel (hexane:ether, 25:1) followed by vacuum distillation (32 C., 184 mTorr) to yield a colorless oil. The product's structure was confirmed by .sup.1H NMR, .sup.13C NMR, and mass spectrometry.
Example 2Synthesis of 4-phenylcyclopentene
(53) A monomer, 4-phenylcyclopentene (4PCP), was synthesized according to the following procedure. The 4-phenyl-1,6-heptadiene (8.0207 g, 46.6 mmol) of Example 1 in anhydrous CH.sub.2Cl.sub.2 (465 mL) was stirred in the presence of Grubbs 1 generation catalyst (G1)(191.5 mg, 0.233 mmol, 0.005 eq.)(see Scheme 1). A dynamic blanket of argon was kept over the solution slowly to promote the removal of ethylene. After 25 hours, the product was concentrated and the crude product was purified by flash chromatography on silica gel (hexane:ether, 25:1) and afforded 4PCP as a colorless oil (5.965 g, 41 mmol, 89% yield). The product's structure was confirmed by .sup.1H NMR, .sup.13C NMR, and mass spectrometry.
(54) The monomer, 4PCP, was synthesized through titanium tetrachloride-mediated diallylation of benzaldehyde followed by standard conditions for ring-closing metathesis of the acyclic diene using Grubbs 1.sup.st generation catalyst, G1 (Scheme 1). Following purification, 4PCP was obtained at approximately 57% yield over two steps.
(55) ##STR00008## ##STR00009##
Example 3Synthesis of poly(4-phenylcyclopentene)
(56) The following is a representative example of the polymerizations provided at Table 1 (P4PCP-6 in Table 1). 0.1961 g (1.36 mmol) and 0.1916 g (1.33 mmol) of 4PCP were each added to separate dry round bottom flasks. The flasks were then lightly purged with argon and placed in a precooled bath at 15 C. A separate HG2 catalyst solution was made at 0.205 g/mL with dry toluene.
(57) To the precooled flasks, 0.96 mL (1.96 mg HG2, 3.13 mol, 0.23 mol %) and 0.093 mL (1.91 mg HG2, 3.04 mol, 0.23 mol %) of the catalyst solution were added respectively and allowed to stir for 12 hours. Twelve hours was chosen due to longer equilibration times at colder temperatures compared to those at warmer temperatures as seen by VT-.sup.1H-NMR.
(58) The solutions were quenched with 0.1 mL (1.04 mmol) of ethyl vinyl ether and allowed to stir at 15 C. for 30 minutes. THF was then added to help dissolve the polymer, and allowed to stir at 15 C. for an additional 10 minutes. From the crude products, an aliquot was taken and diluted in CDCl.sub.3 for .sup.1H-NMR to determine percent conversion. The remaining crude product was passed through a basic alumina column and directly precipitated into an excess of methanol.
(59) The polymers were then isolated and dried overnight in a vacuum over at 50 C. to obtain the duplicate P4PCP-6 samples (M.sub.n=95.6 kg mol.sup.1, =1.60, 84.5% conversion and M.sub.n=89.0 kg mol.sup.1, =1.67, 85.0% conversion). The structures of the polymers were confirmed by .sup.1H NMR, .sup.13C NMR, and mass spectrometry.
(60) TABLE-US-00001 TABLE 1 4PCP polymerization results under varying conditions..sup.a M.sub.n,theo (kg Sample ID Solvent T ( C.) Catalyst Conv. (%).sup.b mol.sup.1).sup.c M.sub.n,SEC (kg mol.sup.1).sup.d .sup.d P4PCP-1 toluene 10 HG2 62.3 0.3 39.1 47.9 2.7 1.51 0.02 P4PCP-2 toluene 5 HG2 67.2 0.3 42.1 47.6 0.5 1.65 0.03 P4PCP-3 toluene 0 HG2 72.2 0.4 45.3 50.9 0.6 1.63 0.01 P4PCP-4 toluene 5 HG2 75.0 0.1 47.1 67.4 1.4 1.60 0.01 P4PCP-5 toluene 10 HG2 78.9 1.2 49.5 72.1 0.5 1.60 0.15 P4PCP-6 toluene 15 HG2 84.6 0.4 53.1 92.3 3.3 1.63 0.03 P4PCP-7 toluene 0 G2 64.3 1.2 40.3 108.0 0.9 1.53 0.01 P4PCP-8 toluene 0 G3 66.2 1.1 41.5 67.1 4.8 1.55 0.04 P4PCP-9 (neat).sup.e 15 HG2 81.2 1.1 51.0 150.9 4.2 1.77 0.01 P4PCP-10 (neat).sup.e 20 HG2.sup.f 81.8 45.4 110.3 1.63 P4PCP-11 THF 0 HG2 74 46.5 76.5 1.47 P4PCP-12 DCM 0 HG2 71 44.5 61.7 1.60 .sup.aUnless otherwise noted; [4PCP].sub.0 = 4.5M, [cat] = 0.23 mol %, rxn time = 12 h. values are based on the standard deviation of duplicate runs .sup.bdetermined by .sup.1H-NMR analysis (CDCl.sub.3) following termination with ethyl vinyl ether. .sup.cbased on monomer-catalyst ratio adjusted for % conversion (supporting information). .sup.ddetermined by SEC (RI) analysis in THF compared to a 10 pt. conventional calibration using narrow dispersity polystyrene standards. .sup.eneat = 6.67M. .sup.f0.26 mol %.
(61) The results of the foregoing catalyst comparison tests (P4PCP-3, 7 and 8) indicated, for these particular tests, that the Hoveyda-Grubbs 2.sup.nd generation catalyst (HG2, Scheme 1) consistently outperformed Grubbs 3.sup.rd generation (G3) and 2.sup.nd generation catalyst (G2) with regards to % conversion at 0 C. after 12 hrs. Therefore, HG2 was chosen for the remaining studies. As shown at Table 2, a series of temperature investigations (P4PCP-(1-6)) were performed at temperatures from 10 C. to 15 C. in toluene ([4PCP].sub.0=4.5 M, 0.23% HG2). Monomer conversion increased linearly as temperature was decreased with 84.6% conversion achieved at 15 C.
(62) TABLE-US-00002 TABLE 2 Results of polymerizations performed in duplicate from Table 1 at varying temperatures, catalysts, and solvents. Temp % Con- M.sub.n, theo.sup.c Mn,.sup.d ID.sup.a ( C.) Cat. Solvent version.sup.b kg/mol kg/mol .sup.d 1a 10 HG2 Toluene 62.6 39.3 45.2 1.52 1b 10 HG2 Toluene 62 38.9 50.6 1.49 avg. 62.3 39.1 47.9 1.51 std dev. 0.42 0.28 3.82 0.02 error 0.30 0.20 2.70 0.02 2a 5 HG2 Toluene 66.9 41.9 47.6 1.63 2b 5 HG2 Toluene 67.5 42.3 48.6 1.68 avg. 67.2 42.1 47.6 1.65 std dev. 0.42 0.28 0.71 0.04 error 0.30 0.20 0.50 0.03 3a 0 HG2 Toluene 72.5 45.5 51.5 1.63 3b 0 HG2 Toluene 71.8 45 50.3 1.62 avg. 72.2 45.3 50.9 1.63 std dev. 0.49 0.35 0.85 0.01 error 0.35 0.25 0.60 0.00 4a 5 HG2 Toluene 75 47 66 1.59 4b 5 HG2 Toluene 75.1 47.1 68.8 1.59 avg. 75 47.1 67.4 1.6 std dev. 0.07 0.07 1.98 0.00 error 0.05 0.05 1.40 0.00 5a 10 HG2 Toluene 80.1 50.2 72.5 1.74 5b 10 HG2 Toluene 77.8 48.8 71.6 1.45 avg. 78.9 49.5 72.1 1.6 std dev. 1.63 0.99 0.64 0.21 error 1.15 0.70 0.45 0.15 6a 15 HG2 Toluene 85 53.3 89 1.67 6b 15 HG2 Toluene 84.3 52.9 95.6 1.6 avg. 84.6 53.1 92.3 1.63 std dev. 0.49 0.28 4.67 0.05 error 0.35 0.20 3.30 0.03 7a 0 G2 Toluene 65.4 41 107.1 1.52 7b 0 G2 Toluene 63.1 39.6 108.9 1.54 avg. 64.3 40.3 108 1.53 std dev. 1.63 0.99 1.27 0.01 error 1.15 0.70 0.90 0.01 8a 0 G3 Toluene 65.1 40.8 62.3 1.51 8b 0 G3 Toluene 67.2 42.1 71.8 1.58 avg. 66.2 41.5 67.1 1.55 std dev. 1.48 0.92 6.72 0.05 error 1.05 0.65 4.75 0.04 9a 15 HG2 Neat.sup.e 80.2 50.3 155 1.78 9b 15 HG2 Neat.sup.e 82.3 51.6 146.7 1.77 avg. 81.2 51 150.9 1.77 std dev. 1.48 0.92 5.87 0.01 error 1.05 0.65 4.15 0.01 .sup.aUnless otherwise noted, polymerizations were run for 12 hours at a constant catalyst loading of 0.23 mol % at 4.5M. error is the standard error of the mean. .sup.bDetermined via .sup.1HNMR of the crude product. .sup.cTheoretically calculated (see Example 6). .sup.dExperimentally measured using SEC-MALS via conventional column calibration. .sup.eNeat = 6.67M.
(63) Equilibrium monomer concentrations were consistent with extrapolated values from the VT-NMR thermodynamic study. For polymerizations performed at 0 C. (P4PCP-(1-3)), SEC determined M.sub.n values were close to theoretical M.sub.n values. At temperatures lower than 0 C. (P4PCP-(4-6)), experimental M.sub.n values were progressively higher than theoretical with the coldest temperatures leading to the largest discrepancy. This was believed to be due to the reduced initiation efficiency of HG2 below 0 C.
(64) However, the resulting M.sub.n values of each duplicate polymerization were very similar regardless of temperature, which was believed to suggest that molar mass can be reproduced consistently and with some degree of predictability under controlled conditions. Comparison of polymerizations in toluene, THF, and DCM at 0 C. (P4PCP-3, 11, 12) demonstrated that, at least in this example, solvent had little effect on conversion percentage although THF resulted in higher M.sub.n and less . Neat polymerizations (P4PCP-9, 10) were performed at 15 and 20 C. but did not improve % conversion, as anticipated. However, these did result in the highest M.sub.n values of 110 and 151 kg mol.sup.1, respectively.
Example 4Hydrogenation
(65) P4PCP-10 (6.1221 g, 42 mmol olefin) was dissolved in 370 mL of o-xylene. A catalytic amount (2 mg) of BHT inhibitor was added followed by tributylamine (38.923 g, 210 mmol) and p-tosylhydrazide (34.9179 g, 187 mmol). The mixture was refluxed for 8 hours.
(66) The solution was then cooled to room temperature and polymer product was precipitated in methanol. The hydrogenated polymer (H2-P4PCP) was isolated by filtration and then reprecipitated. The polymer was then freeze dried from benzene overnight under vacuum (94.4% yield). The structures of the polymers were confirmed by .sup.1H NMR, .sup.13C NMR, and mass spectrometry.
(67) Quantitative homogeneous hydrogenation of P4PCP resulted in a precision ethylene-styrene (ES) copolymer (H.sub.2-P4PCP) with a phenyl branch at every fifth carbon along the backbone. This equated to a perfectly alternating trimethylene-styrene sequence with 71.2% w/w styrene content that is believed to be inaccessible through molecular catalyst copolymerization strategies.
(68) Differential scanning calorimetry confirmed P4PCP and H.sub.2-P4PCP were amorphous materials with similar glass transition temperatures (T.sub.g) of 172 C. Both materials presented well-defined styrenic analogs for application in specialty materials or composites where lower softening temperatures may be desired.
(69) P4PCP-10 (M.sub.n=110 kg mol.sup.1, =1.63) was chosen as a representative sample for further analysis. The backbone olefin microstructure was determined to be 84% trans and 16% cis through inverse gated decoupling .sup.13C-NMR in CDCl.sub.3. Homogeneous hydrogenation of P4PCP-10 was performed with p-tosylhydrazide and tributylamine in refluxing o-xylene for 8 h resulting in quantitative saturation of the backbone.
(70)
(71) Thermogravimetric analysis of P4PCP-10 and H.sub.2-P4PCP was performed under argon and both exhibited good thermal stability with less than 5% weight loss up to 3462 C. and 4012 C., respectively. The results from differential scanning calorimetry (DSC) upon a second heating from 30 to 180 C. at 10 C. min.sup.1 is shown at
(72) In view of the foregoing results, the ROMP of 4-phenylcyclopentene to produce a precision polypentenamer (P4PCP) with a phenyl branch at every 5th carbon was successful. High conversions (80%) and high molar mass (100 kg mol-1) were consistently achieved at cold polymerization temperatures (15 C.) using HG2 catalyst.
(73) Hydrogenation of P4PCP was performed quantitatively under mild homogeneous conditions to afford H2-P4PCP; a precision ES copolymer with exactly 71.2% w/w (40 mol %) styrene and much lower dispersity than ES copolymers produced through molecular catalyst methods. Both systems had excellent thermal stability and the near ambient Tg (17 C.) of these materials was believed to provide an opportunistic styrenic analog.
(74) The methods herein, including those of the foregoing examples, are provided for making a polystyrene-polyethylene-type copolymer analog (which is called hydrogenated poly(4-phenylcyclopentene) or H.sub.2-P4PCP) that has a phenyl branch placed precisely at every 5.sup.th carbon along the polyethylene like backbone (see Scheme 1). For comparison, polystyrene (PS) is believed to have a phenyl branch at precisely every 2.sup.nd carbon. The reduction in phenyl branch periodicity for the system and products provided herein was revealed to dramatically reduce the glass transition temperature (T.sub.g) from 110 C. (PS) to 17 C. (H.sub.2-P4PCP) and embodiments of the products herein remained amorphous. In addition to other uses provided herein, this T.sub.g may permit the materials to be used as dampening material to reduce vibration and noise.
(75) Therefore, it was believed that embodiments of the products herein are prone to improved softening and flexibility at ambient temperatures, and that structural integrity and elasticity may be improved upon, in some instances, by at least partially cross-linking the olefin backbone prior to hydrogenation.
Example 5Sulfonation
(76) Due to the precise and diluted spacing of the phenyl branches of the polymers of the foregoing examples, it was believed that the full sulfonation (i.e. one sulfonate functionality per phenyl branch) of the polymer of these examples could create new materials to rival PSS, due at least in part to the enhanced flexibility of the native polymer.
(77) Preliminary attempts to sulfonate H.sub.2-P4PCP of molar mass ranging from 11-78 kg mol.sup.1 were successful with 80-120% sulfonation achieved as confirmed by elemental analysis, titration, and .sup.1H NMR spectroscopy (see Scheme 2).
(78) ##STR00010##
(79) The higher values of sulfonation obtained by elemental analysis could be attributed to residual sulfuric acid remaining within the polymer prior to analysis. The addition of ionic character to polymeric materials is believed to increase T.sub.g. For highly sulfonated PSS, the T.sub.g raises to temperatures above the thermal decomposition range of the polymer. For the systems herein, having a native material with a much lower T.sub.g, sulfonation also increased T.sub.g to 50 C. (
(80) TABLE-US-00003 TABLE 3 Successfully sulfonated H.sub.2-4PCP of varying molar mass. M.sub.n H.sub.2-P4PCP % % M.sub.n SP4PCP ID [kg mol.sup.1].sup.a) PDI.sup.a) sulfonation.sup.b) sulfonation.sup.c) [kg mol.sup.1].sup.d) Poly-1 11.2 1.50 101.00 104.00 17.5 Poly-2 51.5 1.68 102.00 117.00 80.6 Poly-3 77.8 1.60 96.00 124.00 119.2 .sup.a)Determined by SEC (RI) analysis in THF compared to a 10 pt. conventional calibration using narrow dispersity polystyrene standards. .sup.b)Detemrined via titration. .sup.c)Determined by elemental analysis. .sup.d)Based on percent of sulfonation via titration.
(81) The total removal of water from the sulfonated polymer was difficult even after freeze-drying and annealing under high vacuum in an oven at 150 C. Therefore the T.sub.g reported in
(82) Nevertheless, the T.sub.g for the systems of the foregoing examples places these materials in a unique category having phenylsulfonic acid functionality and an accessible softening temperature. Applications such as flexible electronics, which often couple PSS with PEDOT to create the electrolyte transport layer, are often complicated by the fact that PSS is a high-T.sub.g and brittle material. The material of this example could serve as an opportunistic alternative to PSS for this and other applications.
Example 6Calculations
(83) H and S determinations were made. Based on the Gibbs-Helmholtz equation
G.sup.0=H.sup.0TS.sup.0,
ROMP thermodynamics were analyzed as equilibrium polymerizations with the relationship
(84)
wherein [M].sub.e is the equilibrium monomer concentration at temperature (T) in Kelvin. H is the enthalpy change during polymerization and S.sup.0 is the standard entropy change calculated from the equation above using H=21.34 kJ mol.sup.1, 273 K, [M].sub.e=1.20 M. R is the universal gas constant (8.314 J mol.sup.1 K.sup.1) or 1.99 cal mol.sup.1K.sup.1).
(85) Theoretical molar mass (M.sub.n.theo) calculations also were performed. The equation used for determination of M.sub.n.theo in Table 1 was
(86)
wherein FW.sub.PCP is the formula weight of 4-phenylcyclopentene (144.22 g mol.sup.1), [M].sup.0 is the initial monomer concentration, and [cat] is the catalyst concentration.
(87) Ring-opening metathesis polymerization (ROMP) of 4-phenylcyclopentene (4PCP) was investigated under various conditions. Thermodynamic analysis revealed a polymerization enthalpy and entropy sufficient for high molar mass and conversions at lower temperatures. In these examples, neat polymerization using Hoveyda-Grubbs 2.sup.nd generation catalyst at 15 C. yielded 81% conversion to poly(4-phenylcyclopentene) (P4PCP) with a number average molar mass of 151 kg mol.sup.1 and dispersity of 1.77.
(88) Previous thermodynamic studies on the ROMP of cyclopentene (CP) indicated that monomer/polymer equilibrium may play a much larger role when compared to cyclic alkenes with higher ring strain. Furthermore, the small enthalpic contribution to the Gibbs-Helmholtz equation for ROMP of CP was believed to cause this equilibrium to become much more sensitized to polymerization temperature. The effect that substituents have on the ring strain of CP and its subsequent polymerizability is believed to be less straightforward. For example, hydroxyl functionality at the 4 position of CP is believed to retain sufficient ring strain for polymerization, while an acetoxy functional group on the 3 position is believed to result in no polymer. This phenomenology is believed to be attributed to bond-angle compressions resulting from the gem-dimethyl (Thorpe-Ingold) effect. Recent work by Choi et al. however has showed that substituted cyclopentenes at the 3 position can undergo ROMP through a tandem ring-opening/ring-closing metathesis pathway (Lee, H.-K.; Bang, K.-T.; Hess, A.; Grubbs, R. H.; Choi, T.-L., J. Am. Chem. Soc. 2015, 137, 9262-9265).
(89) To probe the efficacy of the ROMP of 4PCP, variable temperature (VT) .sup.1H-NMR was used to monitor the change in equilibrium monomer concentration [M], as a function of temperature (5 C.<T<15 C.) for a 2.5 M solution (0.23 mol % HG2) in toluene-ds. At each temperature, the conversion of monomer to polymer was monitored until equilibrium was reached. A plot of logarithmic [M], versus inverse temperature (K.sup.1), (
(90) A sufficiently negative H value of 4PCP was believed to suggest that high molar mass and high conversion were possible through temperature reduction and increasing monomer concentration. Therefore a series of polymerizations were performed with varying catalyst, solvent, and temperature (Table 1) to analyze the conversions and molar masses obtained. All samples were terminated with ethyl vinyl ether at the respective polymerization temperatures to prevent depolymerization upon warming. .sup.1H-NMR analysis (CDCl.sub.3) of each sample was performed to determine the percent conversion by integration ratios of the monomer and polymer olefinic proton peaks. (See