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CN-122003450-A - Solution process for producing functionalized polyolefin

CN122003450ACN 122003450 ACN122003450 ACN 122003450ACN-122003450-A

Abstract

The present invention relates to a process for the solution copolymerization to obtain a hydroxy-functionalized polyolefin comprising at least the steps of a) a contacting step for obtaining a mixture of oligomeric aluminum alkyl dialkoxide, wherein the aluminum alkyl dialkoxide is a mixture comprising at least one enol anion fragment, b) a polymerization step of at least one olefin monomer with the mixture obtained at least in step a), c) a deprotection step, wherein the product obtained in step b) is treated with an aliphatic alcohol and/or water and/or a bronsted acid or base solution to obtain a hydroxy-functionalized polyolefin.

Inventors

  • R. Duchateo
  • M. Boya
  • L. Jassinska-Volcker
  • W. Zaote

Assignees

  • SABIC环球技术有限责任公司

Dates

Publication Date
20260508
Application Date
20241010
Priority Date
20231011

Claims (15)

  1. 1. A polymerization process for obtaining a hydroxy-functionalized polyolefin comprising at least the steps of: a) A contacting step for forming a mixture of oligomeric alkyl aluminum dialkoxides, Wherein the alkyl aluminum dialkoxide is a mixture comprising at least one enolic anion fragment, And wherein the contacting step: (i) The process is carried out between the following substances: An aluminum alkyl dienol, which is preferably the reaction product of a hydroxy-functionalized olefin comonomer with a trialkylaluminum, the aluminum alkyl dienol comonomer being represented by the structure according to formula (1): (1) Wherein R 1 、R 2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4 and R 5 are each independently selected from hydrocarbyl groups having 1-9 carbon atoms, And Aluminum alkyl dialkanoates, which are preferably the reaction products of saturated alcohols with trialkylaluminum, represented by the structure according to formula (2): (2) Wherein R 5 and R 6 are each independently selected from hydrocarbyl groups having 1 to 9 carbon atoms; And/or (Ii) The process is carried out between the following substances: aluminum alkyl dialkanoate according to formula (2) And Aluminum alkyl dienols, which are preferably the reaction products of hydroxy-functionalized olefin comonomers with aluminum alkyl dialkanols, which are represented by the structure according to formula (3): (3) Wherein R 1 、R 2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4 、R 5 and R 6 are each independently selected from hydrocarbyl groups having 1-9 carbon atoms; And/or (Iii) The process is carried out between the following substances: Saturated alcohols And Dialkylaluminum enols, which are preferably the reaction products of hydroxy-functionalized olefin comonomers with dialkylaluminum alkoxides, represented by the structure according to formula (4): (4) Wherein R 1 、R 2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4 and R 5 are each independently selected from hydrocarbyl groups having 1-9 carbon atoms, And/or (Iv) The process is carried out between the following substances: Hydroxyl-functional olefin comonomers (enols), And Dialkylaluminum alkoxides, which are preferably the reaction products of saturated alcohols with equimolar amounts of trialkylaluminum or dialkylaluminum hydrides, are represented by the structure according to formula 5: (5) wherein R 5 and R 6 are each independently selected from hydrocarbyl groups having 1 to 9 carbon atoms, And/or (V) The process is carried out between the following substances: the hydroxyl-functional olefin comonomer is described, And The water-soluble polymer of the saturated alcohol, Preferably in a preliminary step, with an equimolar amount of trialkylaluminium relative to the total amount of hydroxyl functionality, B) A polymerization step in the presence of a catalyst system of: At least one olefin monomer represented by CHR 7 =CHR 8 , wherein R 7 and R 8 are each independently selected from hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, optionally wherein R 7 and R 8 form a ring structure, preferably selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, 1-decene, norbornene, vinylidene-norbornene, ethylidene-norbornene, and At least the mixture obtained in step a), The catalyst system comprises: A metal catalyst or catalyst precursor comprising a metal of groups 3 to 10 of the IUPAC periodic Table of elements, A cocatalyst, and Optionally, a scavenger selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and Optionally a chain transfer agent selected from hydrogen or AlR 9 3 、BR 9 3 or ZnR 9 2 , wherein each R 10 is independently selected from hydrogen or C 1 -C 10 hydrocarbyl, Optionally, a second olefin monomer as shown in CHR 7 =CHR 8 , C) A deprotection step wherein the product obtained in step b) is treated with an aliphatic alcohol and/or water and/or a bronsted or alkaline solution to obtain a hydroxy-functionalized polyolefin.
  2. 2. The process according to claim 1, wherein the saturated alcohol used to obtain the aluminum alkyl dialkanoate (2), aluminum alkyl (alkanol) enolate (3), aluminum dialkyl alkoxide (5) and/or used in step a) (v) is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, including their respective isomer structures, preferably methanol, ethanol, propanol, butanol, more preferably methanol, ethanol.
  3. 3. The process according to claims 1-2, wherein the at least one hydroxy-functional olefin comonomer used to obtain the alkyl dienylaluminum (1), the alkyl (alkanol) enolaluminum (3) and the dialkyl enolaluminum (4) and/or for step a) (v) is selected from allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, preferably 3-buten-1-ol, 5-hexen-1-ol and hydroxy-functional cyclostrained cyclic olefins (also referred to as internal olefins), which may typically be e.g. hydroxy-functional norbornene, preferably 5-norbornene-2-methanol.
  4. 4. A process according to claims 1-3, wherein the trialkylaluminum is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, preferably trimethylaluminum, triethylaluminum.
  5. 5. The process according to claims 1-4, wherein the trialkylaluminum used in combination with the hydroxy-functionalized olefin comonomer and the saturated alcohol is the same or different, preferably the same.
  6. 6. The process according to claims 1-5, wherein the metal catalyst or catalyst precursor comprises a group 3-8, more preferably a group 3-6 metal and/or wherein the metal catalyst comprises a metal selected from Ti, zr, hf, V, cr, fe, co, ni, Pd, preferably Zr or Hf, preferably a homogeneous single-site catalyst, more preferably a hafnium complex of a polyvalent aryloxyether or a zirconium complex of a polyvalent aryloxyether, wherein the hafnium complex of a polyvalent aryloxyether is selected from bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydro-anthracene-5-yl) -5- (methyl) phenyl) -2-phenoxy) -1, 3-propanediylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenyl) -2, 3-propanediyldibenzylhydrazine (IV), bis ((2-oxo-3- (dibenzo-1, 3-H-pyrrol-5-yl) -5- (methyl) phenyl) -2-phenoxy) -1, 3-propanediylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -1, 3-propanediyldibenzylhydrazine (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydro-anthracen-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydro-anthracen-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanedibenzylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylhafnium (IV) dichloride, bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylhafnium (IV) bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracen-5-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV) dichloride, bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracen-5-yl) -2- (methyl) phenylbis ((2-oxo-3- (1, 2,3, 6,7,8, 9-octahydro-anthracen-5-yl) -2-phenylbis (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV) dichloride, bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedimethylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -2-phenoxy) -2-pentanediylhafnium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedibenzylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedimethylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedihafnium (IV), and bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedibenzylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -2-phenoxymethyl) -2-cyclohexanedihafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 4-n-butylhafnium (IV) bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 4-n-butyldibenzylhydrazine (IV), bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1, 3-propylhafnium (IV), bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1, 3-propyldibenzylhydrazine (IV), bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1, 4-n-butylhafnium (IV), bis ((2-oxo-3- (3, 6-bis (1-dimethylethyl) -9H-carbazolyl) phenyl) -1, 4-n-butylhafnium (IV), bis ((2-oxo-3- (4-methoxy-3, 5-bis (1, 1-di)) s Methylethyl) phenyl) -2-phenoxy) -1, 4-n-butylhafnium (IV), bis ((2-oxo-3- (4-methoxy-3, 5-bis (1, 1-dimethylethyl) phenyl) -2-phenoxy) -1, 4-n-butyldibenzylhydrazine (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 2-ethyldimethylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 2-ethyldibenzylhydrazine (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 3-propyldimethylhafnium (IV), preferably bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediyldibenzyl (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV) dichloride, (OC-6-33) - [ [2,2' - [1, 4-butanediylbis (oxy- κo) ] bis [3' ',5',5' ' -tris (1, 1-dimethylethyl) [1,1':3',1' ' -terphenyl ] -2' -hydroxy- κo ] ] (2-) ] bis (phenylmethyl) hafnium; Or alternatively Wherein the zirconium complex of the polyvalent aryloxyether is selected from the group consisting of bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenyl) -2-phenoxy) -1, 3-propanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7, 9-octahydroanthracene-5-yl) -5-phenoxy) -1, 3-propanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -1, 3-propanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenoxy) -1, 4-butanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanedibenzylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanedimethylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -1, 4-butanedibenzylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -2-butanedibenzylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2, 4-pentanediylzirconium (IV) dichloride, bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthrac-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedizirconium (IV), bis ((2-oxo-3- (1, 4,6, 8-octahydro-phenyl) -2-phenoxy) -2-zirconium (IV), bis ((2-oxo-3- (1, 2,3,4,6,7,8, 9-octahydroanthracene-5-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedibenzylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedidimethylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedizirconium (IV), and bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) -methylene trans-1, 2-cyclohexanedizirconium (IV), bis ((2-oxo-3- (4-methoxy-3, 5-bis (1, 1-dimethyl) phenyl) -2-phenoxymethyl) -n-butyl-zirconium (IV), bis ((2-oxo-3- (4-methoxy-3, 5-bis (1, 1-dimethylethyl) phenyl) -2-phenoxy) -1, 4-n-butyldibenzyl zirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 2-ethyldimethylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 2-ethyldibenzyl zirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 3-propyldimethylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 3-propyldibenzyl zirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 4-n-butylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) phenyl) -2-phenoxy) -1, 4-n-butyldibenzyl zirconium (IV), bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1 3-propylzirconium (IV) bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1, 3-propylzirconium dibenzyl (IV), bis ((2-oxo-3- (3, 6-bis (1, 1-dimethylethyl) -9H-carbazolyl) phenyl) -2-phenoxy) -1, 4-n-butylzirconium dibenzyl (IV), preferably bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV) dichloride, (OC-6-33) - [ [2,2' ' ' - [1, 4-butanediylbis (oxo- κO) ] bis [3' ',5',5' ' -tris (1, 1-dimethylethyl) [1,1':3',1' ' -terphenyl ] -2' -hydroxy- κO ] ] (2-) ] bis (phenylmethyl) zirconium, preferably bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylzirconium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV) dichloride, bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediyldibenzylhum (IV), more preferably bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV), bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediylhafnium (IV) dichloride, bis ((2-oxo-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxy) -2, 4-pentanediyldibenzyl (IV).
  7. 7. The process according to claim 1-6, wherein the cocatalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO or ammonium salts of fluorinated tetraarylborates or trityl salts, preferably MAO, MMAO, trityltetra (pentafluorophenyl) borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate or tri (alkyl) ammonium tetrakis (pentafluorophenyl) borate.
  8. 8. The process according to claims 1-7, wherein after the deprotection step (c) the recovery step (d) of the functionalized polyolefin is performed by a deashing step in order to separate residues of passivating species such as aluminium oxides and hydroxides from the functionalized polyolefin.
  9. 9. The process according to claims 1-8, wherein the deprotection step c) is performed with a strong bronsted acid, preferably phosphoric acid, or with a weak bronsted acid, preferably an alcohol or water.
  10. 10. The process according to claims 1-9, wherein the deprotection step c) is performed with a base, preferably a bronsted base, more preferably NaOH.
  11. 11. The process according to claims 1-10, wherein the deashing step d) is performed after the deprotection step c).
  12. 12. The process of any one or more of claims 1-11, wherein the amount of hydroxy-functional olefin comonomer in the hydroxy-functional polyolefin obtained in step c) is 0.01-20mol%, preferably 0.02-15mol%, or 0.05-10mol%, or 0.1-5mol%, more preferably 0.02-2mol%, relative to the total molar amount of olefin monomer and hydroxy-functional olefin comonomer in the hydroxy-functional polyolefin.
  13. 13. The process according to claims 1-12, wherein a hydroxy-functionalized copolymer is obtained, preferably a copolymer wherein the first monomer is selected from ethylene and propylene and the second monomer is selected from 3-buten-1-ol, 5-hexen-1-ol and 5-norbornene-2-methanol, more preferably the functionalized copolymer is poly (propylene-co-5-hexen-1-ol), poly (ethylene-co-5-hexen-1-ol), poly (propylene-co-3-buten-1-ol), poly (ethylene-co-3-buten-1-ol) or poly (ethylene-co-5-norbornene-2-methanol).
  14. 14. The process according to claims 1-12, wherein a hydroxy functional terpolymer is obtained, preferably a terpolymer wherein the first monomer is selected from ethylene and propylene, the second monomer is selected from propylene, 1-hexene, 1-octene and norbornene, and the third monomer is selected from 3-buten-1-ol, 5-hexen-1-ol and 5-norbornene-2-methanol, more preferably the functional terpolymer is poly (ethylene-co-propylene-co-5-hexen-1-ol), poly (ethylene-co-1-butene-co-5-hexen-1-ol), poly (ethylene-co-1-hexen-5-hexen-1-ol), poly (ethylene-co-1-octen-5-hexen-1-ol), poly (ethylene-co-norbornene-5-hexen-1-ol), poly (ethylene-co-propylene-3-buten-1-ol), poly (ethylene-co-1-buten-3-buten-1-ol), poly (ethylene-co-1-hexen-3-buten-1-ol), poly (ethylene-co-1-octen-co-3-buten-1-ol), poly (ethylene-co-norbornene-co-5-norbornene-2-methanol), poly (ethylene-co-propylene-co-5-norbornene-2-methanol), poly (ethylene-co-1-buten-co-5-norbornene-2-methanol), poly (ethylene-co-1-hexene-co-5-norbornene-2-methanol), poly (ethylene-co-1-octen-5-norbornene-2-methanol), poly (propylene-co-ethylene-co-5-hexen-1-ol), poly (propylene-co-1-butene-co-5-hexen-1-ol), poly (propylene-co-1-hexen-co-5-hexen-1-ol), poly (propylene-co-ethylene-co-3-buten-1-ol), poly (propylene-co-1-butene-co-3-butene-1-ol) or poly (propylene-co-1-hexene-co-3-butene-1-ol).
  15. 15. The method of any one or more of claims 1-14, wherein the method does not comprise or consist of a ring-opening polymerization process.

Description

Solution process for producing functionalized polyolefin Technical Field The present invention relates to a process for obtaining functionalized polyolefins, in particular hydroxy-functionalized polyolefins, and to functionalized polyolefins. Background WO22106689A1 and Macromolecules 2022, (55), 776-787 disclose polymerization processes for producing hydroxy-functionalized polyolefins using a catalyst system comprising a hafnium or zirconium complex and a cocatalyst selected from the group consisting of MAO, MMAO, DMAO, SMAO or ammonium salts of fluorinated tetraarylboronic acids or trityl salts to polymerize an olefin monomer and at least one passivated hydroxy-functionalized olefin comonomer. However, it has been found that the efficiency of incorporation of trialkylaluminum deactivated hydroxy-functionalized olefin comonomers decreases at higher conversions, particularly in slurry polymerization processes where the functionalized copolymer precipitates during the polymerization. One way to achieve higher conversion of the hydroxy-functionalized olefin comonomer is to use a solution process. However, during the solution polymerization process at higher conversions of the hydroxy-functional olefin comonomer, the viscosity of the polymer solution and subsequently the polymer melt obtained after removal of the solvent increases with the conversion of the hydroxy-functional olefin comonomer, which hampers the processing of the polymer melt after the polymerization reaction. Accordingly, there is a need for a method of producing functionalized polyolefins that overcomes at least one of these drawbacks. EP2524935 discloses a ring-opened polymer of cyclopentene in which the cis proportion of a cyclopentene-derived structural unit is 30% or more, the weight average molecular weight (Mw) is 100,000-1,000,000, and a functional group containing a structure represented by the following general formula (1) or (2) is included at the end of a polymer chain: -Y-H (1) (in the above general formula (1), Y represents an oxygen atom or a sulfur atom). -NH-Q (2) (In the above general formula (2), Q represents a hydrogen atom or a hydrocarbon group or a silyl group which may have a substituent). The process of the present invention includes an addition type olefin polymerization process, sometimes referred to as addition polymerization, as opposed to ring-opening polymerization, more specifically as opposed to ring-opening metathesis polymerization, as disclosed in EP 2524935. More specifically, the present invention includes an addition-type copolymerization step. In other words, the polymerization processes disclosed herein do not include or consist of ring-opening polymerization processes. Disclosure of Invention This object is achieved by the present invention. The present invention therefore relates to a polymerization process for obtaining hydroxy-functionalized polyolefins, comprising at least the following steps: a) A contacting step for forming a mixture of oligomeric alkyl aluminum dialkoxide, wherein the alkoxide anion is a mixture of an enolate anion and an alkoxide anion comprising at least one enolate anion fragment, And wherein the contacting step: (i) The process is carried out between the following substances: An aluminum alkyl dienol, which is preferably the reaction product of a hydroxy-functionalized olefin comonomer with a trialkylaluminum, the aluminum alkyl dienol comonomer being represented by the structure according to formula (1): (1) Wherein R 1、R2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4 and R 5 are each independently selected from hydrocarbyl groups having 1-9 carbon atoms, And Aluminum alkyl dialkanoates, which are preferably the reaction products of saturated alcohols with trialkylaluminum, represented by the structure according to formula (2): (2) Wherein R 5 and R 6 are each independently selected from hydrocarbyl groups having 1 to 9 carbon atoms; And/or (Ii) The process is carried out between the following substances: aluminum alkyl dialkanoate according to formula (2) And Aluminum alkyl dienols, which are preferably the reaction products of hydroxy-functionalized olefin comonomers with aluminum alkyl dialkanols, which are represented by the structure according to formula (3): (3) Wherein R 1、R2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4、R5 and R 6 are each independently selected from hydrocarbyl groups having 1-9 carbon atoms; And/or (Iii) The process is carried out between the following substances: Saturated alcohols And Dialkylaluminum enols, which are preferably the reaction products of hydroxy-functionalized olefin comonomers with dialkylaluminum alkoxides, represented by the structure according to formula (4): (4) Wherein R 1、R2 and R 3 are each independently selected from H and hydrocarbyl groups having 1-9 carbon atoms, and R 4 and R 5 are each independently selec