PROCESS FOR THE PREPARATION OF A BLOCK COPOLYMER COMPRISING A FIRST POLYOLEFIN BLOCK AND A SECOND POLYMER BLOCK AND THE PRODUCTS OBTAINED THEREFROM

• US 20170349710A1
• Filed: 12/17/2015
• Published: 12/07/2017
• Est. Priority Date: 12/17/2014
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Jasinska-Walc, Lidia, Bouyahyi, Miloud, Duchateau, Robbert, Rutkowski, Lukasz Szymon, Zych, Arkadiusz
• Granted Patent: US 10,533,075 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 2410/01 Additive used together with the catalyst, excluding compounds containing Al or B
• CPC Class Codes: C08F 2810/40 taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/06 Oxidation
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides
• CPC Class Codes: C08G 64/18 Block or graft polymers
• CPC Class Codes: C08G 81/027 containing polyester or polycarbonate sequences

Abstract

The present invention relates to a process for the preparation of a block copolymer comprising a first type of polyolefin block and at least one type of second polymer block, the process comprising the steps of: A) polymerizing at least one type of olefin monomer using a catalyst system to obtain a first polyolefin block containing a main group metal on at least one chain end; the catalyst system comprising: i) a metal catalyst or metal catalyst precursor comprising a metal from Group 3-10 of the IUPAC Periodic Table of elements; and ii) at least one type of chain transfer agent; and iii) optionally a co-catalyst; B) reacting the first polyolefin block containing a main group metal on at least one chain end obtained in step A) with at least one type of oxidizing agent and subsequently at least one type of metal substituting agent to obtain a first polyolefin block containing at least one functionalized chain end; C) forming at least one second polymer block on the first polyolefin block, wherein as an initiator the functionalized chain end of the first polyolefin block obtained in step B) is used to obtain the block copolymer.

Claims

1. A process for the preparation of a block copolymer comprising a first type of polyolefin block and at least one type of second polymer block, the process comprising the steps of:

A) polymerizing at least one type of olefin monomer using a catalyst system to obtain a first polyolefin block containing a main group metal on at least one chain end;

the catalyst system comprising;

i) a metal catalyst or metal catalyst precursor comprising a metal from Group 3-10 of the IUPAC Periodic Table of elements; and

ii) at least one type of chain transfer agent; and

iii) optionally a co-catalyst;

B) reacting the first polyolefin block containing a main group metal on at least one chain end obtained in step A) with at least one type of oxidizing agent and subsequently at least one type of metal substituting agent to obtain a first polyolefin block containing at least one functionalized chain end;

C) forming at least one second polymer block on the first polyolefin block, wherein as an initiator the functionalized chain end of the first polyolefin block obtained in step B) is used to obtain the block copolymer and a transesterification reaction is carried out to add a second polymer block to at least one chain end of the first polymer block.

2. The process according to claim 1, wherein step C) of obtaining a block copolymer is carried out by ROP using at least one type of cyclic monomer.

3. The process according to claim 1, wherein step C) of obtaining a block copolymer is carried out by at least one transesterification reaction at a carbonyl group-containing functionality of at least one type of second polymer or wherein step C) of obtaining a block copolymer is carried out by transesterification of at least one type of second polymer comprising at least one carboxylic or carbonic acid ester functionality.

4. The process according to claim 1, wherein step C) of obtaining a block copolymer is carried out by a combination of ROP using at least one type of cyclic monomer and at least one transesterification reaction at a carbonyl group-containing functionality of at least one type of second polymer.

5. The process according to claim 2, wherein during step C) a catalyst for the ROP or transesterification reaction is used.

6. The process according to claim 1, wherein the metal catalyst or metal catalyst precursor used in step A) comprises a metal from Group 3-8 of the IUPAC Periodic Table of elements and/or wherein the metal catalyst or metal catalyst precursor used in step A) comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd.

7. The process according to claim 1, wherein the co-catalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO, fluorinated aryl borane or fluorinated aryl borate.

8. The process according to claim 1, wherein the olefin monomer used in step A) is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, and vinylidene-norbornene and one or more combinations thereof.

9. The process according to claim 2, wherein the cyclic monomer used during ROP in step C) is a polar monomer, selected from the group consisting of a lactone, a lactide, a cyclic oligoester (e.g. a di-ester, a tri-ester, a tetra-ester, a penta-ester or higher oligoesters), an epoxide, an aziridine, a combination of epoxide and/or aziridine and CO₂, a cyclic anhydride, a combination of epoxide and/or aziridine and a cyclic anhydride, a combination of epoxide and/or aziridine and CO₂ and a cyclic anhydride, a cyclic N-carboxyanhydride, a cyclic carbonate, a lactam and one or more combinations thereof.

10. The process according to claim 2, wherein the cyclic monomer used during ROP in step C) is a cyclic monomer comprising a carbonyl group-containing functionality and at least 10 consecutive carbon atoms in the ring.

11. The process according to claim 3, wherein the second polymer block comprising at least carboxylic or carbonic acid ester functionality or a carbonyl group-containing functionality is selected from the group consisting of a polyester, a polycarbonate, a polyamide, a polyurethane, a polyurea, a random or block poly(carbonate-ester), poly(carbonate-ether), poly(ester-ether), poly(carbonate-ether-ester), poly(ester-amide), poly(ester-ether-amide), poly(carbonate-amide), poly(carbonate-ether-amide), poly(ester-urethane), poly(ester-ether-urethane), poly(carbonate-urethane), poly(carbonate-ether-urethane), poly(ester-urea), poly(ester-ether-urea), poly(carbonate-urea), poly(carbonate-ether-urea), poly(ether-amide), poly(amide-urethane), poly(amide-urea), poly(urethane-urea).

12. The process according to claim 1, wherein the chain transfer agent is a main group metal hydrocarbyl or a main group metal hydride.

13. The process according to claim 12, wherein the chain transfer agent is selected from the group consisting of trialkyl boron, dialkyl boron halide, dialkyl boron hydride, diaryl boron hydride, dialkyl boron alkoxide, dialkyl boron aryloxide, dialkyl boron amide, dialkyl boron thiolate, dialkyl boron carboxylate, dialkyl boron phosphide, dialkyl boron mercaptanate, dialkyl boron siloxide, dialkyl boron stannate, alkyl boron dialkoxide, alkyl boron diaryloxide, alkyl boron dicarboxylate, alkyl boron diphosphide, alkyl boron dimercaptanate, alkyl boron disiloxide, alkyl boron distannate, boron hydride dialkoxide, boron hydride diaryloxide, boron hydride diamide, boron hydride dicarboxylate, boron hydride diphosphide, boron hydride dimercaptanate, boron hydride disiloxide, boron hydride distannate, trialkyl aluminum, dialkyl aluminum halide, dialkyl aluminum hydride, dialkyl aluminum alkoxide, dialkyl aluminum aryloxide, dialkyl aluminum amide, dialkyl aluminum thiolate, dialkyl aluminum carboxylate, dialkyl aluminum phosphide, dialkyl aluminum mercaptanate, dialkyl aluminum siloxide, dialkyl aluminum stannate, alkyl aluminum dialkoxide, alkyl aluminum diaryloxide, alkyl aluminum dicarboxylate, alkyl aluminum diphosphide, alkyl aluminum dimercaptanate, alkyl aluminum disiloxide, alkyl aluminum distannate, aluminum hydride dialkoxide, aluminum hydride diaryloxide, aluminum hydride diamide, aluminum hydride dicarboxylate, aluminum hydride diphosphide, aluminum hydride dimercaptanate, aluminum hydride disiloxide, aluminum hydride distannate, trialkyl gallium, dialkyl gallium halide, dialkyl gallium hydride, dialkyl gallium alkoxide, dialkyl gallium aryloxide, dialkyl gallium amide, dialkyl gallium thiolate, dialkyl gallium carboxylate, dialkyl gallium phosphide, dialkyl gallium mercaptanate, dialkyl gallium siloxide, dialkyl gallium stannate, dialkyl magnesium, diaryl magnesium, alkyl magnesium halide, alkyl magnesium hydride, alkyl magnesium alkoxide, alkyl magnesium aryloxide, alkyl magnesium amide, alkyl magnesium thiolate, alkyl magnesium carboxylate, alkyl magnesium phosphide, alkyl magnesium mercaptanate, alkyl magnesium siloxide, alkyl magnesium stannate, dialkyl calcium, alkyl calcium halide, alkyl calcium hydride, alkyl calcium alkoxide, alkyl calcium aryloxide, alkyl calcium amide, alkyl calcium thiolate, alkyl calcium carboxylate, alkyl calcium phosphide, alkyl calcium mercaptanate, alkyl calcium siloxide, alkyl calcium stannate, dialkyl zinc, alkyl zinc halide, alkyl zinc hydride, alkyl zinc alkoxide, alkyl zinc aryloxide, alkyl zinc amide, alkyl zinc thiolate, alkyl zinc carboxylate, alkyl zinc phosphide, alkyl zinc mercaptanate, alkyl zinc siloxide, alkyl zinc stannate, and or more combinations thereof.

14. The process according to claim 1, wherein the oxidizing agent in step B) is selected from the group consisting of O₂, CO, O₃, CO₂, CS₂, COS, R²NCO, R²NCS, R²NCNR¹, CH₂═

C(R²)C(═

O)OR³, CH₂═

C(R²)(C═

O)N(R³)R⁴, CH₂═

C(R²)P(═

O)(OR³)OR⁴, N₂O, R²CN, R²NC, epoxide, aziridine, cyclic anhydride, R³R⁴C═

NR², SO₃, and R²C(═

O)R³, or a combination of NH₃ and NaClO or a combination of H₂O₂ and NaOH.

15. A block copolymer obtained by or obtainable by a process according to claim 1.

16. The process according to claim 12, wherein the chain transfer agent is selected from the group consisting of:

hydrocarbyl aluminum, hydrocarbyl magnesium, hydrocarbyl zinc, hydrocarbyl gallium, hydrocarbyl boron, hydrocarbyl calcium, aluminum hydride, magnesium hydride, zinc hydride, gallium hydride, boron hydride, calcium hydride and one or more combinations thereof.

17. The process according to claim 13, wherein the chain transfer agent is selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum, tri(t-butyl) aluminum di(isobutyl) aluminum hydride, di(n-butyl) magnesium, n-butyl(ethyl)magnesium, benzyl calcium 2,6-di(t-butyl)-4-methyl-phenoxide, dimethyl zinc, diethyl zinc, trimethyl gallium, or triethylboron, 9-borabicyclo(3.3.1)nonane, catecholborane, and diborane and one or more combination thereof.

18. The process according to claim 14, wherein the oxidizing agent in step B) is selected from the group consisting of O₂, O₃, N₂O, epoxide, aziridine, CH₂═

C(R²)C(═

O)OR³, CH₂═

C(R²)(C═

O)N(R³)R⁴, CH₂═

C(R²)P(═

O)(OR³)OR⁴, R²C(═

O)R³, R³R⁴C═

NR², a combination of NH₃ and NaClO or a combination of H₂O₂ and NaOH, where R², R³, R⁴, R⁵ and R⁶ are each independently selected from hydrogen or SiR⁷₃, SnR⁷₃ or a C1-C16 hydrocarbyl, preferably selected from hydrogen or C1-C16 hydrocarbyl;

where each R⁷ is independently selected from hydride, halide or C1-6 hydrocarbyl.