IP Library › Granted Patent US 12,649,840
Granted Patent B2
US 12,649,840 · App. 17/999,232 · Granted Jun 9, 2026

Processes for producing cyclic olefins from polymers and re-polymerization thereof

Inventors: Alexander V. Zabula (Seabrook, TX); Lubin Luo (Houston, TX); Carlos R. Lopez-Barron (Houston, TX); Brian J. Rohde (Houston, TX); Mark K. Davis (Humble, TX); Frank N. Raushel (Baytown, TX); Yong Yang (Kingwood, TX); Alan A. Galuska (Ellijay, GA)
Assignee: ExxonMobil Chemical Patents Inc.
C08J11/16C07C4/22C08G61/08C07C2531/24C08G2261/11C08G2261/122C08G2261/216C08G2261/3321C08G2261/3325C08G2261/418C08J2319/00C08J2365/00
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Quick Facts
Patent No.
US 12,649,840
App. No.
17/999,232
Granted
Jun 9, 2026
Kind
B2
Abstract

In some embodiments, a process for producing a cyclic olefin includes introducing a polymer to a metathesis catalyst in a reaction vessel under reaction conditions. The process includes obtaining a cyclic olefin product comprising the cyclic olefin. In some embodiments, a process for producing a cyclic olefin includes introducing an article comprising a polymer to a metathesis catalyst in a reaction vessel under reaction conditions. The process includes obtaining a cyclic olefin product comprising the cyclic olefin.

Claims (57)

1 . A process for producing a volatile cyclic monoolefin, the process comprising:

introducing an unsaturated polymer comprising a vulcanized polymer to a metathesis catalyst in a reaction vessel under reaction conditions, wherein the vulcanized polymer further comprises a copolymer of polypentenamer and polyoctenamer; and

obtaining a product comprising the volatile cyclic monoolefin.

2 . The process of claim 1 , wherein the copolymer of polypentenamer and polyoctenamer is represented by Formula (IV):

wherein:

n is an integer from 1 to about 25,000;

m is an integer from 1 to about 25,000;

z is an integer from 1 to about 5,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13 ′ R 14 , R 14′ , R 15 , R 15′ , R 16 , and R 16′ is independently hydrogen, C 1 -C 40 hydrocarbyl, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 , R 4 and R 5 , R 5 and R 6 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 join together to form a saturated or unsaturated cyclic C 5 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently hydrogen or an end cap, wherein the end cap is an ether, an amine, an aryl, or a carboxylic acid.

3 . The process of claim 2 , wherein:

n is from about 500 to about 5,000;

m is from about 500 to about 5,000;

z is from about 100 to about 3,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13 ′ R 14 , R 14′ , R 15 , R 15′ , R 16 , and R 16′ is independently hydrogen or C 1 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently the end cap, the end cap is the ether selected from the group consisting of ethyl ether, propyl ether, butyl ether, pentyl ether, and hexyl ether.

4 . The process of claim 1 , wherein the copolymer of polypentenamer and polyoctenamer is represented by Formula (V):

wherein:

n is an integer from 1 to about 25,000;

m is an integer from 1 to about 25,000;

z is an integer from 1 to about 5,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , and R 14′ is independently hydrogen, C 1 -C 40 hydrocarbyl, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 , R 4 and R 5 , R 5 and R 6 , R 11 and R 12 , or R 13 and R 14 , join together to form a saturated or unsaturated cyclic C 5 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently hydrogen or an end cap, wherein the end cap is an ether, an amine, an aryl, or a carboxylic acid.

5 . The process of claim 4 , wherein:

n is from about 500 to about 5,000;

m is from about 500 to about 5,000;

z is from about 100 to about 3,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , and R 14′ is independently hydrogen or C 1 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently the end cap, the end cap is the ether selected from the group consisting of ethyl ether, propyl ether, butyl ether, pentyl ether, and hexyl ether.

6 . A process comprising:

introducing a volatile cyclic monoolefin, chemically recycled from an unsaturated polymer comprising a vulcanized polymer, to a metathesis catalyst in a reaction vessel under polymerization reaction conditions and producing a product that includes a high molecular weight polymer, wherein the vulcanized polymer further comprises a copolymer of polypentenamer and polyoctenamer.

7 . The process of claim 6 , wherein the copolymer of polypentenamer and polyoctenamer is represented by Formula (IV):

wherein:

n is an integer from 1 to about 25,000;

m is an integer from 1 to about 25,000;

z is an integer from 1 to about 5,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , R 14′ , R 15 , R 15′ , R 16 , and R 16′ is independently hydrogen, C 1 -C 40 hydrocarbyl, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 , R 4 and R 5 , R 5 and R 6 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 join together to form a saturated or unsaturated cyclic C 5 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently hydrogen or an end cap, wherein the end cap is an ether, an amine, an aryl, or a carboxylic acid.

8 . The process of claim 7 , wherein:

n is from about 500 to about 5,000;

m is from about 500 to about 5,000;

z is from about 100 to about 3,000;

each of R 1 , R 1 , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , R 14′ , R 15 , R 15′ , R 16 , and R 16′ is independently hydrogen or C 1 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently the end cap, and the end cap is the ether selected from the group consisting of ethyl ether, propyl ether, butyl ether, pentyl ether, and hexyl ether.

9 . The process of claim 6 , wherein the copolymer of polypentenamer and polyoctenamer is represented by Formula (V):

wherein:

n is an integer from 1 to about 25,000;

m is an integer from 1 to about 25,000;

z is an integer from 1 to about 5,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , and R 14′ is independently hydrogen, C 1 -C 40 hydrocarbyl, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 , R 4 and R 5 , R 5 and R 6 , R 11 and R 12 , or R 13 and R 14 , join together to form a saturated or unsaturated cyclic C 5 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently hydrogen or an end cap, wherein the end cap is an ether, an amine, an aryl, or a carboxylic acid.

10 . The process of claim 9 , wherein:

n is from about 500 to about 5,000;

m is from about 500 to about 5,000;

z is from about 100 to about 3,000;

each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 , R 5′ , R 6 , R 6′ , R 7 , R 8 , R 11 , R 11′ , R 12 , R 12′ , R 13 , R 13′ , R 14 , and R 14′ is independently hydrogen or C 1 -C 10 hydrocarbyl; and

each R 9 and R 10 is independently the end cap, and the end cap is the ether selected from the group consisting of ethyl ether, propyl ether, butyl ether, pentyl ether, and hexyl ether.

Continuity (2)
Provisional Application 63032157 · May 29, 2020
Related Publication 20230220179A1 · Jul 13, 2023
References Cited (93)
US 4988764A · Nishio et al. · 1991 [cited by applicant]
US 5312940A · Grubbs et al. · 1994 [cited by applicant]
US 5342909A · Grubbs et al. · 1994 [cited by applicant]
US 5656693A · Ellul et al. · 1997 [cited by applicant]
US 5831108A · Grubbs et al. · 1998 [cited by applicant]
US 5969170A · Grubbs et al. · 1999 [cited by applicant]
US 6111121A · Grubbs et al. · 2000 [cited by applicant]
US 6225432B1 · Weng et al. · 2001 [cited by applicant]
US 6759537B2 · Grubbs et al. · 2004 [cited by applicant]
US 6803429B2 · Morgan et al. · 2004 [cited by applicant]
US 6921735B2 · Hoveyda et al. · 2005 [cited by applicant]
US 7312331B2 · Bertrand et al. · 2007 [cited by applicant]
US 7329758B1 · Grubbs et al. · 2008 [cited by applicant]
US 8063232B2 · Hagadorn et al. · 2011 [cited by applicant]
US 8283419B2 · Hagadorn et al. · 2012 [cited by applicant]
US 8329921B2 · Hagadorn et al. · 2012 [cited by applicant]
US 8372930B2 · Brant et al. · 2013 [cited by applicant]
US 8399725B2 · Brant et al. · 2013 [cited by applicant]
US 8519147B2 · Hagadorn et al. · 2013 [cited by applicant]
US 8524930B2 · Holtcamp et al. · 2013 [cited by applicant]
US 8557902B2 · Holtcamp et al. · 2013 [cited by applicant]
US 8604148B2 · Holtcamp et al. · 2013 [cited by applicant]
US 8623962B2 · Hagadorn et al. · 2014 [cited by applicant]
US 8809563B2 · Holtcamp et al. · 2014 [cited by applicant]
US 9024034B2 · Holtcamp et al. · 2015 [cited by applicant]
US 9181360B2 · Holtcamp et al. · 2015 [cited by applicant]
US 9714393B2 · Ng et al. · 2017 [cited by applicant]
US 10093864B2 · Tandon · 2018 [cited by applicant]
US 10494490B2 · Xiong et al. · 2019 [cited by applicant]
US 10519301B2 · Bohm · 2019 [cited by applicant]
US 20020015519A1 · Tokas et al. · 2002 [cited by applicant]
US 20020053379A1 · Tokas et al. · 2002 [cited by applicant]
US 20020166629A1 · Caster et al. · 2002 [cited by applicant]
US 20030058812A1 · Kendall et al. · 2003 [cited by applicant]
US 20030069374A1 · Grubbs et al. · 2003 [cited by applicant]
US 20030149274A1 · Herrmann et al. · 2003 [cited by applicant]
US 20030186035A1 · Cruce et al. · 2003 [cited by applicant]
US 20030230598A1 · Kendall et al. · 2003 [cited by applicant]
US 20050261451A1 · Ung et al. · 2005 [cited by applicant]
US 20060052487A1 · Cruce et al. · 2006 [cited by applicant]
US 20080064891A1 · Lee · 2008 [cited by applicant]
US 20090076226A1 · Meca et al. · 2009 [cited by applicant]
US 20090306268A1 · Pawlow et al. · 2009 [cited by applicant]
US 20100010161A1 · Arriola et al. · 2010 [cited by applicant]
US 20100069573A1 · Arriola et al. · 2010 [cited by applicant]
US 20100113719A1 · Patton et al. · 2010 [cited by applicant]
US 20100168352A1 · Arriola et al. · 2010 [cited by applicant]
US 20100222513A1 · Arriola et al. · 2010 [cited by applicant]
US 20100324094A1 · Tillekeratne et al. · 2010 [cited by applicant]
US 20110112349A1 · Holtcamp et al. · 2011 [cited by applicant]
US 20120077945A1 · Holtcamp et al. · 2012 [cited by applicant]
US 20140099573A1 · Weitekamp et al. · 2014 [cited by applicant]
US 20150118188A1 · Weitekamp et al. · 2015 [cited by applicant]
US 20160215089A1 · Tuba et al. · 2016 [cited by applicant]
US 20170121242A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121243A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121244A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121245A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121246A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121247A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121248A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121252A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121254A1 · Iaccino et al. · 2017 [cited by applicant]
US 20170121255A1 · Iaccino · 2017 [cited by applicant]
US 20170190806A1 · Obrecht et al. · 2017 [cited by applicant]
US 20180067393A1 · Weitekamp · 2018 [cited by applicant]
US 20180127539A1 · Tuba et al. · 2018 [cited by applicant]
US 20180265607A1 · Kennemur et al. · 2018 [cited by applicant]
US 20180319721A1 · Sangar et al. · 2018 [cited by applicant]
EP 1693357 · 2006 [cited by applicant]
WO WO1998040373 · 1998 [cited by applicant]
WO WO2018232212 · 2018 [cited by applicant]
William J. Neary and Justin G. Kennemur; ACS Macro Letters 2019 8 (1), 46-56; DOI: 10.1021/acsmacrolett.8b00885 (Year: 2019). [cited by examiner]
Liu, Peng, and Chunjin Ai. “Olefin metathesis reaction in rubber chemistry and industry and beyond.” Industrial & Engineering Chemistry Research 57.11 (2018): 3807-3820. (Year: 2018). [cited by examiner]
[cited by applicant]
Alder, R. W. (1996) “Bis(diisopropylamino)carbene,” [cited by applicant]
Amin, S. B. et al. (2008) “Versatile Pathways for in-situ Polyolefin Functionalization with Heteroatoms: Catalytic Chain Transfer,” [cited by applicant]
Bertrand, G. and Bourissou, D. et al. (2000) “Stable Carbenes,” [cited by applicant]
Bertrand, G. and Lavallo, V. et al. (2005) “A Rigid Cyclic (Alkyl)(amino)carbene Ligand Leads to Isolation of Low-Coordinate Transition-Metal Complexes,” [cited by applicant]
Chung, T. C. (2002) “Synthesis of Functional Polyolefin Copolymers with Graft and Block Structures,” [cited by applicant]
Dragutan, V. et.al. (2010) “A Selective Route for Synthesis of Linear Polydicyclopentadien,” [cited by applicant]
Enders, D. et al. (1995) “Preparation, Structure, and Reactivity of 1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, a New Stable Carbene,” [cited by applicant]
Engel, J. and Jensen, V. et al. (2017) “Loss and Reformation of Ruthenium Alkylidene: Connecting Olefin Metathesis, Catalyst Deactivation, Regeneration, and Isomerization,” [cited by applicant]
Feist, J. D. et al. (2020) “Enol Ethers Are Effective Monomers for Ring-Opening Metathesis Polymerization: Synthesis of Degradable and Depolymerizable Poly(2,3-dihydrofuran)” [cited by applicant]
Fogg, D. E. and Higman, C. S. et al. (2016) “Catalyst Decomposition During Olefin Metathesis Yields Isomerization-Active Ruthenium Nanoparticles,” [cited by applicant]
Sytniczuk, A. and Grela, K. et al. (2018) “Sequential Alkene Isomerization and Ring-Closing Metathesis in Production of Macrocyclic Musks from Biomass,” [cited by applicant]
Hermann, W. A. et al. (1996) “N-Heterocyclic Carbenest: Generation under Mild Conditions and Formation of Group 8-10 Transition Metal Complexes Relevant to Catalysis,” [cited by applicant]
Hermann, W. A. et al. (1996) “Heterocyclic Carbenes:† A High-Yielding Synthesis of Novel, Functionalized N-Heterocyclic Carbenes in Liquid Ammonia,” [cited by applicant]
Lopez, R. G. et al. (2007) “Synthesis of Well-Defined Polymer Architectures by Successive Catalytic Olefin Polymerization and Living/Controlled Polymerization Reactions,” [cited by applicant]
Mathers, R. T. et al. (2004) “Cross Metathesis Functionalization of Polyolefin,” [cited by applicant]
Mulhearn, W. D. and Register, R. A. (2017) “Synthesis of Narrow-Distribution, High-Molecular-Weight ROMP Polycyclopentene via Suppression of Acyclic Metathesis Side Reactions,” [cited by applicant]
Tuba, R. et al. (2016) “Synthesis of Recyclable Tire Additives via Equilibrium Ring-Opening Metathesis Polymerization” [cited by applicant]
Zabula, A. V. et al. (2008) “Mono- and Bidentate Benzannulated N-Heterocyclic Germylenes, Stannylenes and Plumbylenes,” [cited by applicant]