Process for preparation of semi-crystalline polyolefinic ionomers

Patent metadata

Field	Value
Publication number	US-11466110-B2
Application number	US-201816956001-A
Country	US
Kind code	B2
Filing date	Dec 24, 2018
Priority date	Dec 22, 2017
Publication date	Oct 11, 2022
Grant date	Oct 11, 2022

Abstract

The present invention relates to a semi-crystalline polyolefinic ionomer and a process for the preparation of a semi-crystalline polyolefinic ionomer.

First claim

The invention claimed is:

1. A process for the manufacture of a semi-crystalline polyolefinic ionomer comprising the steps of:
a1) copolymerizing at least one olefin monomer and at least one masked functionalized olefin monomer in the presence of a catalyst system,
wherein the at least one olefin monomer is represented by CH 2 ═CHR 1 , wherein R 1 is an alkyl group having 1 to 6 carbon atoms,
wherein the at least one masked functionalized olefin monomer is a reaction product of a functionalized olefin monomer represented by the structure according to Formula (I) and a masking agent:

wherein R 2 , R 3 , and R 4 are each independently selected from the group consisting of H and hydrocarbyl with 1 to 16 carbon atoms,
wherein R 5 —[X—(R 6 ) n ] m is a polar functional group containing one or multiple heteroatom containing functionalities X—(R 6 ) n wherein
X is selected from —O—, —S— or —CO 2 — and R 6 is H, and n is 1, or
X is N and R 6 is each independently selected from the group consisting of H and a hydrocarbyl group with 1 to 16 carbon atoms, and n is 2,
wherein R 5 is either —C(R 7a )(R 7b )— or a plurality of —C(R 7a )(R 7b )— groups, wherein R 7a , and R 7b are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms and R 5 comprises 1 to 10 carbon atoms,
wherein R 3 and R 5 may together form a ring structure that is functionalized with one or multiple X—(R 6 ) n ,
where X is attached to either a main chain or side chain of R 5 , where m is an entire number between 1 and 10, and either
b1) treating a product of step a1) with a protic solution containing a metal salt, an ammonium salt or an amine to perform an exchange reaction, or
a2) contacting a product of a1) with a Brønsted acid solution to abstract a residue derived from the masking agent from a functionalized olefin copolymer of step a1) to obtain a semi-crystalline functionalized olefin copolymer comprising the at least one olefin monomer and the functionalized olefin monomer, and either
b2) treating a product of step a2) with a monovalent metal salt, a monocationic ammonium salt or a monofunctional amine, or
b3) treating a product of step a2) with a multi-valent metal salt, a polycationic ammonium salt or a polyfunctional amine.

2. The process of claim 1 , wherein the at least one olefin monomer is selected from the group consisting of propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinyl cyclohexane and 1-octene.

3. The process of claim 1 , wherein the functionalized olefin monomer is selected from the group consisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid.

4. The process of claim 1 , wherein an amount of the at least one masked functionalized olefin monomer in step a1) is from 0.01 to 30 mol %, with respect to a total molar amount of the at least one olefin monomer and the at least one masked functionalized olefin monomer.

5. The process of claim 1 , wherein the masking agent is selected from trialkyl aluminum complexes, dialkyl magnesium complexes, dialkyl zinc complexes or trialkyl boron complexes.

6. The process of claim 1 , wherein in step b1) or b2) the metal salt or monovalent metal salt is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate, bromate or EDTA salt of a metal selected from one or more of lithium, sodium, potassium or silver.

7. The process according to claim 1 , wherein in step b3) the multi-valent metal salt is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate, bromate or EDTA salt of magnesium, calcium, strontium, barium, zinc, copper, tin, silver, iron, chromium, aluminum or gallium.

8. The process of claim 1 , wherein, the Brønsted acid solution used in step a2) comprises inorganic and/or organic acids.

9. The process of claim 1 , wherein the at least one olefin monomer is a first and a second olefin monomer, wherein the first and second olefin monomers are different and wherein an amount of the first olefin monomer is at least 75 mol %, and an amount of second olefin monomer is at most 25 mol %, the mol % based on a total molar amount of first and second olefin monomer.

10. The process of claim 9 wherein the first olefin monomer is propylene and the second olefin monomer is 1-hexene.

11. A semi-crystalline polyolefinic ionomer obtained by the process of claim 1 .

12. The semi-crystalline polyolefinic ionomer of claim 11 wherein,
said at least one olefin monomer is selected from the group consisting of propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinyl cyclohexane and 1-octene,
said functionalized olefin monomer is selected from the group consisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid,
wherein functionalized groups in the semi-crystalline polyolefinic ionomer are cross-linked by means of one or more selected from the group consisting of monovalent metal ions, monocationic ammonium ions, monofunctional amines, multi-valent metal ions, polycationic ammonium ions and polyfunctional amines.

13. The semi-crystalline polyolefinic ionomer according to claim 11 comprising between 0.1 and 10 molar equivalent, of a metal salt, an ammonium salt or an amine with respect to a mol % of functionalized olefin monomer incorporated in the semi-crystalline polyolefinic ionomer.

14. The process of claim 1 , wherein the at least one olefin monomer is propylene, 1-hexene, or a combination thereof.

15. The process of claim 1 , wherein the functionalized olefin monomer is buten-1-ol, 3-buten-2-ol, 10-undecene-1-ol, 4-pentenoic acid or 10-undecenoic acid.

16. The process of claim 1 , wherein an amount of the at least one masked functionalized olefin monomer in step a1) is from 0.02 to 20 mol %, with respect to a total molar amount of the at least one olefin monomer and the at least one masked functionalized olefin monomer.

17. The process of claim 1 , wherein the monofunctional amine is selected from NH 3 , Me 2 NH, NMe 3 , EtNH 2 , Et 3 N, or BuNH 2 .

18. The process of claim 1 , wherein the moncationic ammonium salt is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate or bromate salt of NH 4 + , Et 3 NH + , or Bu 4 N + .

19. The process according to claim 1 , wherein the polyfunctional amine is selected from ethylene diamine, N,N,N′,N′-tetramethyl ethylene diamine, 1,3-diaminopropane, hexamethylenediamine, piperazine, diethylene triamine, N,N,N′,N″,N″-pentamethyl diethylene triamine, or polyethylenimine.

Assignees

• Sabic Global Technologies Bv

Inventors

• Jasinska-Walc Lidia
• Duchateau Robbert
• Bouyahyi Miloud
• Ginzburg Anton
• Troisi Enrico

Classifications

• C08F2/06

  Organic solvent · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2800/10

  as molar percentages · CPC title

• C08F2410/07

  Catalyst support treated by an anion, e.g. Cl-, F-, SO42- · CPC title

• C08F220/64

  Acids; Metal salts or ammonium salts thereof · CPC title