Methods for producing telechelic polyolefins from terpene initiators
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/00
C08F-012/08
C08F-110/10
C08F-004/16
C08F-002/38
C08F-004/14
C08F-004/52
출원번호
US-0910844
(2013-06-05)
등록번호
US-9187581
(2015-11-17)
발명자
/ 주소
Stokes, Casey D.
Chang, Young
출원인 / 주소
Chevron Oronite Company LLC
대리인 / 주소
Jones Day
인용정보
피인용 횟수 :
0인용 특허 :
79
초록
Provided herein are methods for the preparation of telechelic polyolefins via polymerization reaction with a terpene initiator.
대표청구항▼
1. A method for producing a telechelic polyolefin, comprising contacting a terpene initiator with a Lewis acid in the presence of one or more monomers; wherein the terpene initiator contains (a) one or more tertiary carbons containing a leaving group, and (b) one or more functional groups, wherein t
1. A method for producing a telechelic polyolefin, comprising contacting a terpene initiator with a Lewis acid in the presence of one or more monomers; wherein the terpene initiator contains (a) one or more tertiary carbons containing a leaving group, and (b) one or more functional groups, wherein the one or more functional groups are bonded to a primary or secondary carbon and are unmodified under polymerization conditions; andwherein the terpene initiator is: wherein: A1 and A2 are each independently a leaving group or H, wherein at least one of A1 and A2 is a leaving group;each X is independently ═O, —NC, —NCO, —OCN, —SH, —SRA, —S(O)RA, —S(O)2RA, —SCN, —NO2, or —OS(O)2RA, wherein each RA is independently alkyl, alkenyl, or alkenyl, and each X is independently bonded to a secondary carbon; andn is an integer from 1-3. 2. The method of claim 1, wherein the telechelic polymer produced has the following formula: wherein: is: wherein: B1 and B2 independently are H or a bond to P, wherein at least one of B1 and B2 is a bond to P;each X is independently ═O, —NC, —NCO, —OCN, —SH, —SRA, —S(O)RA, —S(O)2RA, —SCN, —NO2, or —OS(O)2RA, wherein each RA is independently alkyl, alkenyl, or alkynyl, and each X is independently bonded to a secondary carbon; andn is an integer from 1-3;each P is independently a divalent polyolefin group;each E is independently an end-cap group; andq is an integer from 1-2. 3. The method of claim 1, wherein the leaving group is, independently at each occurrence, —Cl, —Br, —I, or —OC(O)RN, wherein RN is alkyl having 1 to 6 carbons. 4. The method of claim 1, wherein n is 1. 5. The method of claim 1, wherein at least one of A1 and A2 is H. 6. The method of claim 1, wherein the terpene initiator contains 10 carbon atoms, excluding any carbon atoms that are a part of the one or more leaving groups or one or more functional groups. 7. The method of claim 1, further comprising adding one or more quenching agents. 8. The method of claim 7, wherein the quenching agent is: (a) allyltrimethylsilane;(b) methallyltrimethylsilane;(c) 1,1-diphenylethylene;(d) furan or a substituted furan;(e) thiophene or a substituted thiophene;(f) triphenylamine;(g) a compound having the following formula: wherein: RPY1 and RPY2 are each independently in each —(CRPY1RPY2)— unit selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms;m is an integer from 1 to 20; andXPY is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, alkoxy, heteroaryl, nitro, ureido, —OC(O)RPY3, —C(O)RPY4, —C(O)ORPY5, —C(O)NRPY6RPY7, —P(RPY8)3, —P(ORPY9)3, —SRPY10, —OSO3RPY11, and —S(O)RPY12;wherein RPY3 is alkyl or alkenyl; and RPY4, RPY5, RPY7, RPY8, RPY9, RPY10, RPY11, and RPY12 are each independently alkyl;(h) a compound having the following formula: wherein: R1 through R8 are each independently hydrogen, alkyl from 1 to 20 carbon atoms, aryl from 6 to about 20 carbon atoms, alkaryl from about 7 to 30 carbon atoms, or aralkyl from about 7 to 30 carbon atoms;R is hydrogen, alkyl from 1 to 20 carbon atoms, aryl from 6 to about 20 carbon atoms, alkaryl from about 7 to 30 carbon atoms, or aralkyl from about 7 to 30 carbon atoms; andXa is oxygen or sulfur;with the proviso that, when R is hydrogen or methyl, then R1, R2, R7 and R8 must be other than hydrogen unless one of R1 and R2 and one of R7 and R8 are each independently branched alkyl of about 3 to 20 carbon atoms, aryl, alkaryl or aralkyl;(i) a compound having the following formula: R1—S—R2 wherein R1 and R2, are each, independently, hydrocarbyl;(j) a compound having the following formula: RSA—S—RSB wherein RSA and RSB are each, independently, alkyl, aryl, aralkyl, alkaryl, wherein: XS is halo or a pseudohalide;RSX is alkyl or aryl;RS3 is tert-butyl; andRS4 and RS5 are each, independently, alkyl, aryl, aralkyl, or alkaryl;(k) a compound having the following formula: wherein: RPH1 and RPH2 are each, independently in each —(CRPH1RPH2)— unit, H or alkyl, and p is an integer from 0-20, wherein:(1) if p is 0, then RPH3 and RPH4 are each, independently, alkyl, and XPH is H;(2) if p is 1, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, or wherein RPH5-RPH7 are each, independently, alkyl or aryl;(3) if p is 2, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or wherein A is or a single bond, RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each, independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, or when —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, form a ring; and(4) if p is 3-20, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkaryloxy, —OH, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or —NRPHXRPHY; wherein A is or a single bond, RPHX and RPHY are each, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, or —C(O)RPHZ, wherein RPHZ is H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, —ORPH8, or —NRPH10RPH11; RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl; or(l) butadiene. 9. The method of claim 2, wherein the end-cap group is: wherein Xb is a halide; (d) a 1-substituted-1,1-diaryl ethylene group;(e) furyl or a substituted furyl;(f) thienyl or a substituted thienyl;(g) triphenylamino; wherein: RPY1 and RPY2 are independently in each —(CRPY1RPY2)— unit selected from the group consisting of hydrogen and alkyl from 1 to 6 carbon atoms;m is an integer from 1 to 20; andXPY is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, alkoxy, heteroaryl, nitro, ureido, —OC(O)RPY3, —C(O)RPY4, —C(O)ORPY5, —C(O)NRPY6RPY7, —P(RPY8)3, —P(ORPY9)3, —SRPY10,—OSO3RPY11, and —S(O)RPY12;wherein RPY3 is alkyl or alkenyl; and RPY4, RPY5, RPY7, RPY8, RPY9,RPY10, RPY11, and RPY12 are each independently alkyl; wherein RSA is alkyl, aryl, aralkyl, alkaryl, wherein: XS is halo or a pseudohalide;RSX is alkyl or aryl;RS3 is tert-butyl; andRS4 and RS5 are each, independently, alkyl, aryl, aralkyl, or alkaryl; wherein: RPH1 and RPH2 are each, independently in each —(CRPH1RPH2)— unit, H or alkyl, and p is an integer from 0-20, wherein:(1) if p is 0, then RPH3 and RPH4 are each, independently, alkyl, and XPH is H;(2) if p is 1, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, or wherein RPH5-RPH7 are each, independently, alkyl or aryl;(3) if p is 2, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or wherein A is or a single bond, RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each, independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, or when —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, form a ring; and(4) if p is 3-20, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkaryloxy, —OH, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or —NRPHXRPHY; wherein A is or a single bond, RPHX and RPHY are each, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, or —C(O)RPHZ, wherein RPHZ is H alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, —ORPH8, or —NRPH10RPH11; RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl; or(k) allyl. 10. The method of claim 2, wherein P is wherein t is an integer from 2-20,000. 11. The method of claim 1, wherein the one or more monomers is isobutene. 12. The method of claim 1, wherein the one or more monomers is styrene. 13. The method of claim 1, wherein the Lewis acid is a titanium halide, an aluminum halide, a boron halide, or an alkyl aluminum halide. 14. The method of claim 1, wherein the Lewis acid is TiCl4. 15. The method of claim 1, wherein the method is performed in the presence of one or more electron donors. 16. The method of claim 15, wherein the one or more electron donors is: wherein R1A, R1B, R1C, R1D, and R1E are each, independently, hydrogen or hydrocarbyl; or R1A and R1B, or R1B and R1C, or R1C and R1D, or R1D and R1E independently form a fused aliphatic ring of about 3 to about 7 carbon atoms or a fused aromatic ring of about 5 to about 7 carbon atoms. 17. The method of claim 16, wherein the one or more electron donors is 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 2-methylpyridine, or pyridine. 18. The method of claim 1, wherein the method is performed in the presence of a common ion salt or common ion salt precursor. 19. The method of claim 18, wherein the common ion salt precursor is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, or tetra-n-butylammonium iodide. 20. The method of claim 7, wherein greater than 90% of the monomer is consumed prior to adding the one or more quenching agents. 21. The method of claim 7, wherein one or more aliquots of additional monomer are added to the polymerization after the initial monomer charge, wherein each individual aliquot of additional monomer is consumed or partially consumed prior to adding a subsequent aliquot of additional monomer or adding the one or more quenching agents. 22. The method of claim 1, wherein the Lewis acid is deactivated with one or more terminators. 23. The method of claim 7, wherein the Lewis acid is deactivated with one or more terminators after adding the one or more quenching agents. 24. The method of claim 2, wherein the Lewis acid is deactivated with one or more terminators and E is a tert-halide. 25. The method of claim 1, wherein the telechelic polyolefin has a polydispersity index of less than 1.9. 26. The method of claim 1, wherein the monomer is polymerized under quasiliving polymerization conditions. 27. The method of claim 1, wherein the terpene initiator is derived by hydrohalogenation of a unsaturated terpene. 28. A compound having the following formula: wherein: is: wherein: B1 and B2 independently are H or a bond to P, wherein at least one of B1 and B2 is a bond to P;each X is independently —OH, —NC, —NCO, —OCN, —SH, —SRA, —S(O)RA, —S(O)2RA, —SCN, —NO2, —OS(O)2RA, or ═O, wherein each RA is independently alkyl, alkenyl, or alkynyl, and each X is independently bonded to a primary or secondary carbon; andn is an integer from 1-3;each P is independently a divalent polyolefin group;each E is independently an end-cap group; andq is an integer from 1-2. 29. The compound of claim 28, wherein X is —OH. 30. The compound of claim 28, wherein n is 1. 31. The compound of claim 28, wherein X is bonded to a primary carbon. 32. The compound of claim 28, wherein the end-cap group is: wherein Xb is a halide; (d) a 1-substituted-1,1-diaryl ethylene group;(e) furyl or a substituted furyl;(f) thienyl or a substituted thienyl;(g) triphenylamino; wherein: RPY1 and RPY2 are independently in each —(CRPY1RPY2)— unit selected from the group consisting of hydrogen and alkyl from 1 to 6 carbon atoms;m is an integer from 1 to 20; andXPY is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, alkoxy, heteroaryl, nitro, ureido, —OC(O)RPY3, —C(O)RPY4, —C(O)ORPY5, —C(O)NRPY6RPY7, —P(RPY8)3, —P(ORPY9)3, —SRPY10, —OSO3RPY11, and S(O)RPY12;wherein RPY3 is alkyl or alkenyl; and RPY4, RPY5, RPY7, RPY8, RPY9, RPY10, RPY11, and RPY12 are each independently alkyl; wherein RSA is alkyl, aryl, aralkyl, alkaryl, wherein: XS is halo or a pseudohalide;RSX is alkyl or aryl;RS3 is tert-butyl; andRS4 and RS5 are each, independently, alkyl, aryl, aralkyl, or alkaryl; wherein: RPH1 and RPH2 are each, independently in each —(CRPH1RPH2)— unit, H or alkyl, and p is an integer from 0-20, wherein:(1) if p is 0, then RPH3 and RPH4 are each, independently, alkyl, and XPH is H;(2) if p is 1, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, or wherein RPH5-RPH7 are each, independently, alkyl or aryl;(3) if p is 2, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and XPH is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or wherein A is or a single bond, RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each, independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, or when —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, form a ring; and(4) if p is 3-20, then RPH3 and RPH4 are each, independently H, alkyl, or alkoxy, and X is H, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkaryloxy, —OH, —F, —Cl, —Br, —I, —At, —CN, —NC, —NCO, —OCN, —NCS, —SCN, —OC(O)RPH8, —C(O)ORPH9, —C(O)NRPH10RPH11, or —NRPHXRPHY; wherein A is or a single bond, RPHX and RPHY are each, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, C(O)RPHZ, wherein RPHZ is H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, —ORPH8, or NRPH10RPH11; RPH5 to RPH7 are each, independently, alkyl, alkenyl, alkynyl, alkaryl, aralkyl, aryl, heteroaryl, alkoxy, hydroxy, —NRPH10RPH11, —F, —Cl, —Br, —I, or —At, RPH8 is alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl, and RPH9 to RPH11 are each, independently, H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl; or(k) allyl. 33. The compound of claim 28, wherein P is wherein t is an integer from 2-20000. 34. The compound of claim 28, wherein the compound has a polydispersity index of less than 1.9. 35. The compound of claim 28, wherein X is bonded to a secondary carbon.
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Kennedy Joseph P. (Akron OH) Goodall Brian L. (Akron OH) Lubnin Alexander V. (Akron OH), Aldehyde-telechelic polyisobutylenes, catalytic method for preparing the same with high conversion and selectivity, and.
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Cheradame Herve M. (Latronche NJ FRX) Lundberg Robert D. (Bridgewater NJ) Chen Frank J. (Edison NJ) Habimana Jean de la Croix (Grenoble FRX), Direct synthesis by cationic polymerization of nitrogen-containing polymers.
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Stokes, Casey D.; Storey, Robson F.; Harrison, James J., Living and quasiliving cationic telechelic polymers quenched by N-substituted pyrrole and methods for their preparation.
Kennedy Joseph P. (510 St. Andrew Cir. Akron OH 44313) Faust Rudolf (#5 1515 Brittain Cir. Akron OH 44310), Living catalysts, complexes and polymers therefrom.
Stokes, Casey D.; Simison, Kelby; Storey, Robson F.; Harrison, James J., Method for preparing polyolefins containing a high percentage of exo-olefin chain ends.
Kennedy Joseph P. (Akron OH) Weyenberg Donald R. (Midland MI) Wilczek Lech (Akron OH) Wright Antony P. (Rhodes MI), Method of preparing allyl-terminated polyisobutylene.
Kennedy Joseph P. (Akron OH) Smith Robert A. (Akron OH) Ross ; Jr. Louis R. (Akron OH), Novel telechelic polymers, block copolymers and processes for the preparation thereof.
Harrison, James J.; Ruhe, Jr., William R.; Nelson, Kenneth D., Polymeric dispersants prepared from copolymers of low molecular weight polyisobutene and unsaturated acidic reagent.
Chiefari, John; Mayadunne, Roshan Tyrrel; Moad, Graeme; Rizzardo, Ezio; Thang, San Hoa, Polymerization process with living characteristics and polymers made therefrom.
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Matyjaszewski Krzysztof ; Coca Simion ; Gaynor Scott G. ; Nakagawa Yoshiki ; Jo Seong Mu, Preparation of novel homo- and copolymers using atom transfer radical polymerization.
Stokes, Casey D.; Storey, Robson F.; Harrison, James J., Process for preparing terminally functionalized living and quasiliving cationic telechelic polymers.
Darren B. Dressen ; Anthony Kreft ; Dennis Kubrak ; Charles William Mann ; Michael A. Pleiss ; Gary Paul Stack ; Eugene D. Thorsett, Pyroglutamic acid derivatives and related compounds which inhibit leukocyte adhesion mediated by VLA-4.
Lewandowski, Kevin M.; Fansler, Duane D.; Wendland, Michael S.; Gaddam, Babu N.; Heilmann, Steven M., Ring-opened azlactone chain transfer agents for radical polymerization.
Cheradame Herve M. (Latronche NJ FRX) Lundberg Robert D. (Bridgewater NJ) Chen Frank J. (Edison NJ) Habimana Jean de la Crois (Grenoble FRX), Terminally-substituted polymeric compositions from cationically polymerizable monomers and initiators.
Kennedy Joseph P. (Akron OH) Puskas Judit E. (Akron OH) Kaszas Gabor (Akron OH) Hager William G. (Akron OH), Thermoplastic elastomers of isobutylene and process of preparation.
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