阅读说明：本技术 制备乙烯和丙烯离聚物的方法 (Process for preparing ethylene and propylene ionomers ) 是由 M·鲍雅伊 L·甲辛斯卡-沃尔克 R·达查特奥 于 2018-12-24 设计创作，主要内容包括：本发明涉及一种乙烯和丙烯离聚物和制备乙烯和丙烯离聚物的方法。(The present invention relates to an ethylene and propylene ionomer and a method of preparing the ethylene and propylene ionomer.)

1. A process for making ethylene and propylene ionomers comprising the steps of:

a1) copolymerizing ethylene, propylene and at least one masked functionalized olefin monomer in the presence of a catalyst system,

wherein the masked functionalized olefin monomer is the reaction product of a functionalized olefin monomer represented by the structure according to formula (I):

wherein R is²、R³And R⁴Each independently selected from H and hydrocarbyl groups having 1 to 16 carbon atoms,

wherein R is⁵-[X-(R⁶)_n]_mIs a polar functional group containing a function X- (R) containing one or more hetero atoms⁶)_nWherein

X is selected from-O-, -S-or-CO₂-, and R⁶Is H, and n is 1, or

X is N, and R⁶Each independently selected from H and hydrocarbyl groups having 1 to 16 carbon atoms, and n is 2,

wherein R is⁵is-C (R)^7a)(R^7b) -or more-C (R)^7a)(R^7b) A group in which R^7aAnd R^7bEach independently selected from H or a hydrocarbyl group having 1 to 16 carbon atoms, and R⁵Containing from 1 to 10 carbon atoms in the molecule,

wherein R is³And R⁵May be formed together with one or more X- (R)⁶)_nThe structure of the functionalized ring(s),

wherein X is connected to R⁵Wherein m is an integer of 1 to 10, preferably 1 or 2, and

b1) treating the product of step a1) with a protic solution containing a metal salt, an ammonium salt or an amine to effect an exchange reaction, or

a2) Contacting the product of a1) with a Bronsted acid solution capable of extracting the residues originating from the masking agent from the functionalized ethylene and propylene copolymer of step a1) to obtain a functionalized ethylene and propylene copolymer, and

b2) treating the product of step a2) with a monovalent metal salt, a monocationic ammonium salt or a monofunctional amine, or

b3) Treating the product of step a2) with a polyvalent metal salt, a polycationic ammonium salt or a polyfunctional amine.

2. The process according to claim 1, wherein in step a1), the ethylene to propylene weight ratio is from 20:80 to 70:30, preferably from 25:75 to 60: 40.

3. The process according to claim 1 or 2, wherein the at least one functionalized olefin monomer is selected from allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1, 2-diol, 5-hexen-1-ol, 5-hexen-1, 2-diol, 7-octen-1-ol, 7-octen-1, 2-diol, 9-decen-1-ol, 10-undecen-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid, preferably 3-buten-1-ol, 3-buten-2-ol, 2, 10-undecen-1-ol, 4-pentenoic acid and 10-undecenoic acid.

4. The process according to any one or more of claims 1 to 3, wherein the amount of functionalized olefin monomer in step a1) is 0.01 to 30 mol%, preferably 0.02 to 20 mol% or 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, relative to the total molar amount of ethylene, propylene and functionalized olefin monomer.

5. The method according to any one or more of claims 1 to 4, wherein the masking agent is selected from trialkylaluminum complexes, dialkylmagnesium complexes, dialkylzinc complexes or trialkylboron complexes, preferably triisobutylaluminum.

6. The method according to any one or more of claims 1 to 5, wherein in step b1) or b2), the 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 and silver,

and/or

The monofunctional amine is selected from NH₃、Me₂NH、NMe₃、EtNH₂、Et₃N、BuNH₂，

And/or

The ammonium salt being NH₄ ⁺、Et₃NH⁺、Bu₄N⁺Fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate or bromate.

7. The process according to any one or more of claims 1 to 6, wherein in step b1) or b3) the polyvalent 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,

and/or

The polyfunctional amine is selected from the group consisting of ethylenediamine, N, N, N ', N' -tetramethylethylenediamine, 1, 3-diaminopropane, hexamethylenediamine, piperazine, diethylenetriamine, N, N, N ', N' -pentamethyldiethylenetriamine, and polyethyleneimine.

8. The process according to any one or more of claims 1 to 7, wherein the Bronsted acid solution used in step a2) comprises an inorganic and/or organic acid, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, phosphoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, citric acid, ethylenediaminetetraacetic acid, or a chelate containing partially neutralized carboxylic acids, such as EDTA salts, in particular disodium edetate (disodium salt of EDTA), or a combination thereof.

9. Ethylene and propylene ionomers obtainable by the process according to any one or more of claims 1 to 8.

10. The ethylene propylene ionomer according to claim 9,

the weight ratio of ethylene to propylene in the polymer is from 20:80 to 70:30, preferably from 25:75 to 60:40, and

the at least one functionalized olefin monomer is selected from allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1, 2-diol, 5-hexen-1-ol, 5-hexen-1, 2-diol, 7-octen-1-ol, 7-octen-1, 2-diol, 9-decen-1-ol, 10-undecen-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid, preferably 3-buten-1-ol, 3-buten-2-ol, 10-undecen-1-ol, 3-buten-1-ol, 4-pentenoic acid and 10-undecenoic acid,

wherein the functional groups in the ionomer are crosslinked by means of one or more selected from monovalent metal ions, mono-cationic ammonium ions, mono-functional amines, polyvalent metal ions, multi-cationic ammonium ions and multi-functional amines.

11. The ethylene and propylene ionomer according to claim 9 or 10 comprising 0.1-10 molar equivalents, preferably 0.2-8 molar equivalents, further preferably 0.4-5 molar equivalents of metal salt, ammonium salt or amine, relative to the mol% of the functionalized olefin monomer introduced in the copolymer.

12. The ethylene and propylene ionomer according to any one or more of claims 9-11, wherein the content of the functionalized olefin monomer is 0.01-30 mol%, preferably 0.02-20 mol% or 0.05-10 mol%, relative to the total amount of the olefin monomer and the functionalized olefin monomer in the copolymer.

13. The ethylene and propylene ionomer according to any one or more of claims 9-12 comprising 0.1-100mol equivalents, preferably 0.1-10mol equivalents, preferably 0.2-8mol equivalents, further preferably 0.4-5mol equivalents of metal salt, ammonium salt or amine, relative to mol% of the functionalized olefin monomer introduced in the copolymer.

14. The ethylene and propylene ionomer of any one or more of claims 9-13 comprising at least one or two types of reversible crosslinks.

Examples

¹H NMR characterization

By carrying out at 125 deg.C¹³C and¹h NMR analysis to determine ethylene content and percent functionalization. The sample was dissolved in deuterated tetrachloroethane (TCE-D2) containing Butylated Hydroxytoluene (BHT) as a stabilizer at 130 ℃. Spectra were recorded in a 5mm tube on a Bruker Avance 500 spectrometer equipped with a cryogenically cooled probe head operating at 125 ℃.

Chemical shifts are reported in ppm units as compared to tetramethylsilane and are determined with reference to residual solvent protons.

Differential Scanning Calorimetry (DSC)

On DSC Q100 from TA Instruments at 5 ℃ min^-1Heating rate ofThermal analysis was performed. Heating to 210 deg.C and at 10 deg.C/min^-1After cooling to about-40 c, the first and second runs were recorded. All copolymers were found to be semi-crystalline as determined by DSC. The enthalpy of fusion was calculated as the area under the peak of the melting transition in DSC.