EP-4735455-A1 - USE OF TRANSITION METAL CATALYST TO PRODUCE LINEAR ETHYLENE/POLAR COPOLYMERS IN A HIGH PRESSURE PROCESS

Abstract

Processes for polymerizing ethylene and one or more polar comonomers and optionally one or more (C 3 −C 12 )α-olefins, and optionally an aluminum compound, in the presence of the catalyst system to form an ethylene-based copolymer in a high pressure reactor at a pressure of greater than 1000 barg and a temperature of greater than 100°C, wherein the catalyst system comprises a transition metal catalyst.

Inventors

• AUYEUNG, Evelyn
• ICIARTE, Rebecca E.
• REPOVZ, Maiah
• KARJALA, JR., Thomas Wesley
• EWART, SEAN W.
• FONTAINE, PHILIP P.
• BROWN, Hayley A.
• SPINNEY, Heather A.
• SENECAL, Todd D.
• GARZA GONZALEZ, Alejandro J.
• NETT, ALEX J.
• FRANKEL, Alexandra E.

Assignees

• Dow Global Technologies LLC

Dates

Publication Date

20260506

Application Date

20240626

Claims (1)

1. 85349-WO-PCT/DOW 85349 WO CLAIMS 1. A polymerization process comprising: polymerizing ethylene, one or more polar comonomers, optionally one or more (C 3 −C 12 )α-olefins, and optionally an aluminum species in the presence of the catalyst system to form an ethylene-based copolymer in a high pressure reactor at a pressure of greater than 1000 barg and a temperature of greater than 100°C, wherein the catalyst system comprises a transition metal catalyst. 2. The polymerization process according to claim 1, wherein the aluminum species comprises aluminoxane or alkyl aluminum, or combinations of aluminoxane and alkyl aluminum. 3. The polymerization process of claim 1 or claim 2, wherein the transition metal catalyst comprises nickel(II) or palladium(II). 4. The polymerization process of any one of the preceding claims, wherein the transition metal catalyst or transition metal procatalyst comprises nickel(II) or palladium(II), and has a structure according to formula (I). where: M is nickel(II) or palladium(II); X is a ligand chosen from (C1−C40)hydrocarbyl, (C 1 −C 40 )heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , −Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , −Ge(R C ) 3-Q (OR C ) Q , −P(R C )2-W(OR C )W, −P(O)(R C )2-W(OR C )W, −N(R C )2, −NH(R C ), −N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , −NHSi(R C ) 3 , −OR C , −SR C , −NO 2 , −CN, −CF 3 , −OCF 3 , −S(O)R C , −S(O) 2 R C , −OS(O) 2 R C , −N=C(R C ) 2 , −N=CH(R C ), −N=CH2, −N=P(R C )3, −OC(O)R C , −C(O)OR C , −N(R C )C(O)R C , −N(R C )C(O)H, −NHC(O)R C , −C(O)N(R C )2, −C(O)NHR C , −C(O)NH 2 , a halogen, or a hydrogen, wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a 85349-WO-PCT/DOW 85349 WO substituted or unsubstituted (C 1 −C 30 )heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2; each Y is a Lewis base, wherein X and Y are optionally linked; P is phosphorous; R 1 is independently selected from the group consisting of –H, (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, −Si(R C )3, −Si(R C )3- Q(OR C )Q, -OSi(R C )3-Q(OR C )Q, -Ge(R C )3-Q(OR C )Q, −P(=O)(R P )2, -P(R C )2- W(OR C ) W , -P(O)(R C ) 2-W (OR C ) W , −Ge(R C ) 3 , −P(R P ) 2 , −N(R N ) 2 , −OR C , −SR C , −NO2, −CN, −CF3, R C S(O)−, R C S(O)2−, −N=C(R C )2, R C C(O)O−, R C OC(O)−, R C C(O)N(R)−, (R C )2NC(O)−, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, −Si(R C )3, −Ge(R C )3, −P(R P )2, −N(R N )2, −OR C , −SR C , −NO2, −CN, −CF3, R C S(O)−, R C S(O)2−, (R C ) 2 C=N−, R C C(O)O−, R C OC(O)−, R C C(O)N(R N )−, (R C ) 2 NC(O)−, or halogen; R 2 , R 3 , and R 4 are independently selected from a substituted (C 1 −C 30 )hydrocarbyl, unsubstituted (C 1 −C 30 )hydrocarbyl, substituted (C 1 −C 30 )heterohydrocarbyl, unsubstituted (C 1 −C 30 )heterohydrocarbyl, −Si(R C )3-Q(OR C )Q, -OSi(R C )3-Q(OR C )Q, -Ge(R C )3-Q(OR C )Q, -P(R C )2- W(OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -NH(R C ) 2 , -OR C , -SR C , - NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , - N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R)C(O)R C , -C(O)N(R C )2, or a halogen, wherein each R C is independently a substituted or unsubstituted (C 1 −C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 −C 30 ) heterohydrocarbyl; Q is 0, 1, 2, or 3 and W is 0, 1, or 2; and 85349-WO-PCT/DOW 85349 WO R 5 and R 6 are independently selected from a substituted (C 1 −C 30 )hydrocarbyl, unsubstituted (C1−C30)hydrocarbyl, substituted (C1−C30)heterohydrocarbyl, or unsubstituted (C1−C30)heterohydrocarbyl; and where: optionally, R 5 and R 6 are linked to form a ring structure; optionally, R 2 and R 3 are linked to form a ring structure; or optionally, R 3 and R 4 are linked to form a ring structure. 5. The polymerization process claim 4, wherein R 5 and R 6 are independently (C1−C20)alkyl, (C6−C20)aryl, or substituted (C6−C20)aryl. 6. The polymerization process any one of claim 4 or claim 5, wherein Y is pyridine, substituted pyridine, sulfoxide, trialkyl, triaryl phosphine, trialkyl, triaryl phosphine oxide, substituted heterocycle, unsubstituted heterocycle, aliphatic ketone, aliphatic amine, alkyl ether, or cycloalkyl ether. 7. The polymerization process any one of claims 4 to 6, wherein R 2 , R 3 , and R 4 are (C1−C18)alkyl or –H. 8. The polymerization process any one of claims 4 to 7, wherein R 1 is a radical of formula (II), (III), or (IV). 9. The polymerization process of any one of claims 4 to 8, wherein X is a substituted or unsubstituted (C1−C30)hydrocarbyl, a substituted or unsubstituted (C1−C30)heterohydrocarbyl. 10. The polymerization process of any one or the preceding claims, wherein the polar monomers comprise one or more alkyl acrylate monomers. 11. The polymerization process of any one or the preceding claims, wherein the alkyl acrylate is methyl acrylate, ethyl acrylate, n-butyl acrylate, or t-butyl acrylate. 12. The polymerization process of any one or the preceding claims, wherein temperature is from greater than 100°C to 250°C. 13. The polymerization process of any one or the preceding claims, wherein pressure is from greater than 1000 barg to 5000 barg. 14. An ethylene-based polymer produced from the polymerization process of either of claims 9 to 12. 15. A procatalyst according to any structure of this disclosure.

Description

85349-WO-PCT/DOW 85349 WO USE OF TRANSITION METAL CATALYST TO PRODUCE LINEAR ETHYLENE/POLAR COPOLYMERS IN A HIGH PRESSURE PROCESS CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application Serial No. 63/511,257 filed June 30, 2023, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD [0002] Embodiments of the present disclosure generally relate to ethylene and polar comonomer polymerization processes to produce linear ethylene copolymers, and, more specifically, to polymerization processes conducted at high temperatures and high pressures that incorporate catalyst systems having transition metal catalysts. BACKGROUND [0003] Commercially, ethylene/acrylate copolymers are formed through high-pressure and/or high-temperature radical processes and have a highly branched microstructure similar to that of low-density polyethylene (LDPE). Methods for copolymerizing ethylene and vinyl monomers containing a polar group, e.g. vinyl acetate and (meth)acrylates, by radical polymerization at high temperature (> 100 °C) under high pressure (> 1000 barg) are well known. These methods, however, result in the production of copolymers with relatively low thermal resistance (low melting temperature due to their low crystallinity and high degree of long-chain branching). [0004] Coordination catalysis in solution provides routes to highly linear ethylene/acrylate copolymers with structures similar to that of linear low-density polyethylene (LLDPE). The linear ethylene/acrylate copolymers formed by coordination catalysis exhibit greater crystallinity and higher thermal resistance than those of the copolymers formed through the radical processes. Both Ni and Pd catalysts have been reported for the copolymerization of ethylene and acrylate monomers in solution at relatively low pressures of ethylene (10-50 barg); however, the reported catalyst efficiencies are typically quite low. The reported Ni and Pd catalysts also exhibit significant deactivation in solution at temperatures > 120 °C and the Mw of the copolymers decreases precipitously at temperatures above 90 °C. 85349-WO-PCT/DOW 85349 WO SUMMARY [0005] Ongoing needs exist to create an improved process for the copolymerization of ethylene and acrylate comonomers to give highly linear copolymers. This process should promote both high rates of ethylene copolymerization activity and high incorporation of the alkylacrylate comonomer to create highly linear copolymers. The linear ethylene/alkylacrylate copolymers may exhibit improved molecular weight distribution and increased melt temperatures. Solution-based processes with Ni and Pd catalysts produce highly linear copolymers, but at low rates. These rates can be improved by introducing the Ni or Pd catalyst to a high pressure (> 1000 barg) and high temperature (> 100 °C) reactor, where the copolymerization reaction occurs in super-critical ethylene. This leads to the production of highly linear copolymers at increased rates and higher molecular weights. [0006] Embodiments of this disclosure includes a polymerization process. The process includes polymerizing ethylene, one or more polar comonomers, optionally one or more (C3−C12)α-olefins, and optionally an aluminum species in the presence of the catalyst system to form an ethylene-based copolymer in a high pressure reactor at a pressure of greater than 1000 barg and a temperature of greater than 100°C, wherein the catalyst system comprises a transition metal catalyst. [0007] In one or more embodiments, the transition metal catalyst comprises nickel(II) or palladium(II). In some embodiments, the transition metal catalyst or transition metal procatalyst comprises nickel(II) or palladium(II), and has a structure according to formula (I). [0008] M is nickel(II) or palladium(II); X is a ligand chosen from (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, -OSi(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −NH(RC), −N(Si(RC)3)2, -NRCSi(RC)3, −NHSi(RC)3, −ORC, −SRC, −NO2, −CN, −CF3, −OCF3, −S(O)RC, −S(O)2RC, −OS(O)2RC, −N=C(RC)2, −N=CH(RC), −N=CH2, −N=P(RC)3, −OC(O)RC, −C(O)ORC, −N(RC)C(O)RC, −N(RC)C(O)H, −NHC(O)RC, −C(O)N(RC)2, −C(O)NHRC, −C(O)NH2, a halogen, or a hydrogen, wherein each RC is independently a substituted or unsubstituted (C1- 85349-WO-PCT/DOW 85349 WO C30)hydrocarbyl, or a substituted or unsubstituted (C1−C30)heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2. [0009] In formula (I) each Y is a Lewis base, wherein X and Y are optionally linked. P is phosphorous. [0010] In formula (I), R1 is independently selected from the group consisting of –H, (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, −Si(RC)3, −Si(RC)3-Q(ORC)Q, -OSi(RC)3- Q(ORC)Q, −Ge(RC)3-Q(ORC)Q , −P(=O)(RP)2, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −Ge(RC)3, −P(RP)2, −N(RN)2, −ORC, −SRC, −NO2, −CN, −CF3, RCS(O)−, RCS(O)2−, −N=C(RC)2, RCC(O)O−, RC