Methods of producing mono- and multi-functional polymers from terpene-based initiators
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-010/10
C08F-002/38
C08F-008/14
C08F-002/00
C08F-110/10
출원번호
US-0179393
(2011-07-08)
등록번호
US-8969484
(2015-03-03)
발명자
/ 주소
Stokes, Casey D.
Chang, Young A.
McDougall, Patrick J.
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 mono- and multi-functional telechelic polyolefins via polymerization reaction with a terpene-based initiator.
대표청구항▼
1. A method for producing a telechelic polymer, comprising contacting a compound of formula I: DL-T)n Iwith a Lewis acid in the presence of one or more monomers, wherein:D is alkaryl, aralkyl, or Yp, where Y is aryl and p is an integer from 1-4;each L, independently, is: wherein each A, independent
1. A method for producing a telechelic polymer, comprising contacting a compound of formula I: DL-T)n Iwith a Lewis acid in the presence of one or more monomers, wherein:D is alkaryl, aralkyl, or Yp, where Y is aryl and p is an integer from 1-4;each L, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andthe oxygen is bonded to T;each T, independently, is a terpene; wherein at least one of the tertiary carbons of the terpene contain a leaving group; andeach n, independently, is an integer from 1-6. 2. The method of claim 1, wherein D is alkaryl or aralkyl. 3. The method of claim 1, wherein D is alkaryl of 7-20 carbons. 4. The method of claim 1, wherein D is aralkyl of 7-20 carbons. 5. The method of claim 1, wherein D is Z(Y)r; wherein: Y, independently, is aryl;Z is hydrocarbyl;L is bonded to a Y of the Z(Y)r; andr is an integer from 1 to 3. 6. The method of claim 1, wherein D is Yp, wherein Y is aryl and p is an integer from 1-4. 7. The method of claim 6, wherein p is 1. 8. The method of claim 6, wherein Y is phenyl. 9. The method of claim 1, wherein L is: 10. The method of claim 9, wherein A is a bond. 11. The method of claim 1, wherein n is an integer from 1-4. 12. The method of claim 1, wherein T is a monoterpene, wherein at least one of the tertiary carbons of the monoterpene contains a leaving group. 13. The method of claim 1, wherein the terpene is not substituted, except for the at least one of the tertiary carbons that contains a leaving group. 14. The method of claim 1, wherein the terpene is not cyclic. 15. The method of claim 1, wherein T has the formula (i), (ii), or (iii): wherein B1 and B2 are each, independently, a leaving group or —H; wherein at least one of B1 and B2 is a leaving group; andif T has formula (i), T is substituted with 1-3 substituents. 16. The method of claim 15, wherein one of B1 and B2 is —H. 17. The method of claim 15, wherein T is: 18. The method of claim 1, wherein the leaving group is —Cl or —Br. 19. The method of claim 1, wherein the compound of formula I has the following formula: and n is an integer from 1-4. 20. The method of claim 19, wherein T is a monoterpene, wherein one or more of the tertiary carbons of the monoterpene contain a leaving group. 21. The method of claim 20, wherein T is: wherein B1 is a leaving group. 22. The method of claim 21, wherein the leaving group is —Cl or —Br. 23. The method of claim 1, further comprising adding one or more quenching agents. 24. The method of claim 23, 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 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 alkyl;(h) a compound having the following formula: wherein:R1 through R8 are 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; andX 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 or R2 and one of R7 or R8 is independently branched alkyl of about 3 to 20 carbon atoms, aryl, alkaryl or aralkyl;(i) a compound having the following formula: R1XS—R2X wherein R1X and R2X, are each, independently, hydrocarbyl;(j) a compound having the following formula: RSAS—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, andp 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:A1 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, andRPH9 to RPH11 are each, independently, —H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl,orwhen —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, may 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:A1 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;(l) butadiene or isoprene; or wherein:Y is carbon or silicon;R1 is hydrocarbyl; andR2-R4 are each, independently, hydrogen or hydrocarbyl. 25. The method of claim 1, wherein the method produces a compound of formula VII: wherein:D is alkaryl, aralkyl, or Yp, where Y is aryl and p is an integer from 1-4;each L, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andthe oxygen is bonded to T;each T, independently, is a terpene;each P, independently, is a polyolefin group;each E, independently, is an end-cap group;n and m are integers, wherein (1) the sum of n and m is 1 to 6; and(2) n is at least 1; andeach s, independently, is an integer from 1-2. 26. The method of claim 25, wherein P is wherein t is an integer from 2-20,000. 27. The method of claim 1, wherein the Lewis acid is a titanium halide, aluminum halide, boron halide, or an alkyl aluminum halide. 28. The method of claim 1, wherein the Lewis acid is TiCl4. 29. The method of claim 1, wherein the method is performed in the presence of one or more electron donors. 30. The method of claim 29, 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. 31. The method of claim 30, wherein the one or more electron donors are 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 2-methylpyridine, or pyridine. 32. The method of claim 1, wherein the method is performed in the presence of a common ion salt or common ion salt precursor. 33. The method of claim 32, wherein the common ion salt precursor is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, or tetra-n-butylammonium iodide. 34. The method of claim 23, wherein greater than 90% of the monomer is consumed prior to adding the quenching agent. 35. The method of claim 1, 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 quenching agent. 36. The method of claim 1, wherein the Lewis acid is deactivated with one or more terminators. 37. The method of claim 23, wherein the Lewis acid is deactivated with one or more terminators after adding the one or more quenching agents. 38. The method of claim 25, wherein the compound of formula VII has a polydispersity index of less than 2.5. 39. The method of claim 1, wherein the monomer is polymerized under quasiliving polymerization conditions. 40. The method of claim 1, wherein the monomer is isobutylene. 41. The method of claim 1, wherein at least two monomers are used. 42. The method of claim 41, wherein the at least two monomers are isobutylene and styrene. 43. The telechelic polymer produced by the method of claim 1. 44. A method for producing a telechelic polymer comprising contacting a compound of formula VIII: HO-T-(P-E)s VIIIwith a compound of formula IX: D-(L1)n IXwherein:D is hydrocarbyl;each T, independently, is a terpene;each P, independently, is a polyolefin group;each E, independently, is an end-cap group;each L1, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andLG is a leaving group;n is an integer from 1-6; ands is an integer from 1-2. 45. The method of claim 44, wherein D is hydrocarbyl of 1-25 carbons. 46. The method of claim 44, wherein D is alkyl, aralkyl, or alkaryl. 47. The method of claim 44, wherein D is aryl. 48. The method of claim 44, wherein D is phenyl. 49. The method of claim 44, wherein LG is —Cl, —Br, —OH, or —OC(O)RA, wherein RA is hydrocarbyl. 50. The method of claim 44, wherein L1 is: 51. The method of claim 50, wherein A is a bond. 52. The method of claim 44, wherein n is an integer from 1-4. 53. The method of claim 44, wherein T is a monoterpene. 54. The method of claim 44, wherein T is not substituted. 55. The method of claim 44, wherein T has the formula (i), (ii), or (iii): wherein (1) if T has the formula (i), then T is substituted with 1-3 substituents and(2) s is 1 or 2; wherein: if s is 1, then one of D1 and D2 is H and the other is P-E; andif s is 2, then each of D1 and D2, independently, is P-E. 56. The method of claim 55, wherein s is 1. 57. The method of claim 55, wherein T is: 58. The method of claim 44, wherein P is polyisobutylene. 59. The method of claim 44, wherein the compound of formula VIII is: wherein P is a polyolefin group and E is an end cap group; andthe compound of formula IX: wherein LG is a leaving group and n is 1-4. 60. The method of claim 44, wherein E is: 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 alkyl; wherein:RSA is alkyl, aryl, aralkyl, alkaryl, 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, andp is an integer from 0-20, wherein:(a) if p is 0, then RPH3 and RPH4 are each, independently, alkyl, and XPH is —H;(b) 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;(c) 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:A1 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, andRPH9 to RPH11 are each, independently, —H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl,orwhen —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, may form a ring; and(d) 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:A1 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, andRPH9 to RPH11 are each, independently, —H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl; wherein:RPZ1 and RPZ2 are independently in each —(CRPZ1RPZ2)— unit, hydrogen or alkyl from 1 to 6 carbon atoms;s is an integer from 2 to 20; andZPZ1 is —F, —Cl, —Br, —I, —At, —CN, —NC, —N3, —NCO, —OCN, —NCS or —SCN; wherein RP is halo or hydrocarbyl of 1-20 carbon atoms optionally substituted with halo or pseudohalo;(8) furan or a furan substituted with hydrocarbyl or substituted hydrocarbyl; or(9) thiophene or a thiophene substituted with hydrocarbyl or substituted hydrocarbyl. 61. The method of claim 44, wherein E is (3) pyrrole or N-hydrocarbylpyrrole, wherein the hydrocarbyl contains 1-20 carbon atoms;(4) —S—RSA, wherein RSA is hydrocarbyl of 1-20 carbon atoms optionally substituted with halo or pseudohalo; wherein R is hydrocarbyl of 1-20 carbon atoms optionally substituted with halo or pseudohalo;(6) haloalkyl or pseudohaloalkyl;(7) —CH2CH═CHCH2—X, wherein X is halo; or wherein RP is halo or hydrocarbyl of 1-20 carbon atoms optionally substituted with halo or pseudohalo. 62. The method of claim 44, wherein the method produces a compound of formula VIIa: wherein:D is hydrocarbyl;each L, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andthe oxygen is bonded to T;each T, independently, is a terpene;each P, independently, is a polyolefin group;each E, independently, is an end-cap group;n is an integer from 1-6; andeach s, independently, is an integer from 1-2. 63. The telechelic polymer produced by the method of claim 44. 64. A compound of formula VII: wherein:D is alkaryl, aralkyl, or Yp, where Y is aryl and p is an integer from 1-4;each L, independently, is: wherein each A, independently, is hydrocarbylene or a bond; and the oxygen is bonded to T;each T, independently, is a terpene;each P, independently, is a polyolefin group;each E, independently, is an end-cap group;n and m are integers, wherein (1) the sum of n and m is 1 to 6; and(2) n is at least 1; andeach s, independently, is an integer from 1-2. 65. The compound of claim 64, wherein D is aralkyl or alkaryl. 66. The compound of claim 64, wherein D is alkaryl of 7-20 carbons. 67. The compound of claim 64, wherein D is aralkyl of 7-20 carbons. 68. The compound of claim 64, wherein D is Z(Y)r, wherein: Y, independently, is aryl;Z is hydrocarbyl;L is bonded to a Y of the Z(Y)r; andr is an integer from 1 to 3. 69. The compound of claim 64, wherein D is Yp, wherein Y is aryl and p is an integer from 1-4. 70. The compound of claim 69, wherein Y is phenyl. 71. The compound of claim 64, wherein L is: 72. The compound of claim 71, wherein A is a bond. 73. The compound of claim 64, wherein m is 0. 74. The compound of claim 64, wherein the sum of n and m 1-4. 75. The compound of claim 64, wherein T is a monoterpene. 76. The compound of claim 64, wherein the terpene is not substituted. 77. The compound of claim 64, wherein the terpene is not cyclic. 78. The compound of claim 66, wherein T has the formula (i), (ii), or (iii): wherein: (1) if T has the formula (i), then T is substituted with 1-3 substituents and(2) s is 1 or 2; wherein: if s is 1, then one of D1 and D2 is H and the other is P-E; andif s is 2, then each of D1 and D2, independently, is P-E. 79. The compound of claim 78, wherein s is 1. 80. The compound of claim 78, wherein T is: 81. The compound of claim 64, wherein the compound of formula VII has the following formula: 82. The compound of claim 81, wherein T is a monoterpene. 83. The compound of claim 82, wherein the compound of formula VII has the following formula: 84. The compound of claim 64, wherein the compound of formula VII has the following formula: 85. The compound of claim 64, wherein the compound of formula VII has the following formula: 86. The compound of claim 64, wherein P is polyisobutylene. 87. The compound of claim 64, wherein E is: 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 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, andp is an integer from 0-20, wherein:(a) if p is 0, then RPH3 and RPH4 are each, independently, alkyl, and XPH is —H;(b) 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;(c) 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:A1 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, andRPH9 to RPH11 are each, independently, —H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl,orwhen —O—(CRPH1RPH2)p—XPH is ortho to RPH4, then XPH and RPH4, together, with the atoms to which XPH and RPH4 are attached, may form a ring; and(d) 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:A1 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, andRPH9 to RPH11 are each, independently, —H, alkyl, alkenyl, alkynyl, alkaryl, aryl, or heteroaryl; wherein:RPZ1 and RPZ2 are independently in each —(CRPZ1RPZ2)— unit, hydrogen or alkyl from 1 to 6 carbon atoms;s is an integer from 2 to 20; andZPZ1 is —F, —Cl, —Br, —I, —At, —CN, —NC, —N3, —NCO, —OCN, —NCS or —SCN; wherein RP is halo or hydrocarbyl of 1-20 carbon atoms optionally substituted with halo or pseudohalo;(8) furan or a furan substituted with hydrocarbyl or substituted hydrocarbyl; or(9) thiophene or a thiophene substituted with hydrocarbyl or substituted hydrocarbyl. 88. The compound of claim 64, wherein E is wherein X is a halide. 89. A compound of formula X: wherein:D is hydrocarbyl;each L, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andthe oxygen is bonded to T;each L1, independently, is: wherein each A, independently, is hydrocarbylene or a bond; andLG is a leaving groupeach T, independently, is a terpene;each P, independently, is a polyolefin group;each E, independently, is an end-cap group;n and m are integers, wherein: (1) the sum of m and n is 2-6; and(2) m is at least 1; and(3) n is at least 1; andeach s, independently, is an integer from 1-2.
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이 특허에 인용된 특허 (79)
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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.
Albert Rossi ; Jacob Emert ; David Edward Gindelberger ; Jon Edmond Stanat ; James Peter Stokes ; Jaimes Sher, Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267).
Knoll Konrad (Mannheim DEX) Bronstert Klaus (Carlsberg DEX) Bender Dietmar (Schifferstadt DEX), Preparation of hydrocarbons and polymers with allylic chloride end groups Friedel-Crafts catalyst.
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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