阅读说明：本技术 制备官能化乙烯和丙烯共聚物的方法 (Process for preparing functionalized ethylene and propylene copolymers ) 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：本发明涉及一种制造官能化乙烯和丙烯共聚物组合物的方法。本发明进一步涉及这样的官能化乙烯和丙烯共聚物组合物。(The present invention relates to a process for the manufacture of a functionalized ethylene and propylene copolymer composition. The invention further relates to such functionalized ethylene and propylene copolymer compositions.)

1. A process for making a functionalized ethylene and propylene copolymer composition comprising the steps of:

a) 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

b) treating the product obtained in step a) with a Bronsted acid solution, optionally containing a metal or ammonium salt, and capable of extracting the residue originating from the masking agent; and combining the resulting functionalized ethylene and propylene copolymer with a crosslinking enhancer selected from the group consisting of: a combination of at least two of a polyol, a polyamine, a polyacid, a polyether, a polyester, a polycarbonate, a polyamide, a polyurethane, a polyurea, a polysaccharide, a polypeptide, and the crosslinking enhancer, wherein the crosslinking enhancer has a functionality of at least 2.

2. The process according to claim 1, wherein in step a) 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 the functionalized olefin monomer in step a) is from 0.01 to 30 mol%, preferably from 0.02 to 20 mol% or from 0.05 to 10 mol%, more preferably from 0.1 to 5 mol%, relative to the total molar amount of the olefin and the 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 1-5, wherein the crosslinking enhancer is selected from the group consisting of ethylene glycol, glycerol, pentaerythritol, mucic acid, galactaric acid, carbohydrates, ethylenediamine, diethylenetriamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, polyethyleneimine, maleic acid, succinic acid, tartaric acid, citric acid, polyacrylic acid, poly (ethylene-co-acrylic acid), polyvinyl acetate, poly (ethylene-co-vinyl acetate), polyvinyl alcohol, poly (ethylene-co-vinyl alcohol), polyethylene oxide, polypropylene oxide, poly (ethylene oxide-co-propylene oxide), poly (ethylene carbonate), poly (propylene carbonate), polycaprolactone, poly (ethylene tridecanoate), polylactide, polybutylene adipate, polybutylene, citric acid, polyacrylic acid, polyethylene imine, maleic acid, succinic acid, tartaric acid, citric acid, poly (ethylene-co-acrylic acid), poly (ethylene-co-vinyl acetate), poly, Polybutylene terephthalate, polyamide-6, polyamide-4, 6, polyamide-6, and combinations of at least two of the foregoing crosslinking enhancers.

7. The process according to any one or more of claims 1 to 6, wherein the amount of the crosslinking enhancer is from 0.01 to 10 wt. -%, preferably from 0.03 to 7 wt. -%, more preferably from 0.05 to 5 wt. -%, based on the combined weight of the functionalized ethylene and propylene copolymer and the crosslinking enhancer.

8. Functionalized ethylene and propylene copolymer composition obtainable by the process according to any one or more of claims 1 to 10.

9. A functionalized ethylene and propylene copolymer composition comprising:

i) from 90 to 99.99 wt%, preferably from 93 to 99.97 wt%, more preferably from 95 to 99.95 wt% of a functionalized ethylene and propylene copolymer of ethylene, propylene and at least one functionalized olefin monomer selected from the group consisting of: 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, 4-pentenoic acid and 10-undecenoic acid,

ii)0.01 to 10 wt.%, preferably 0.03 to 7 wt.%, more preferably 0.05 to 5 wt.% of at least one crosslinking enhancer selected from the group consisting of: polyols, polyamines, polyacids, polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyureas, polysaccharides, polypeptides, wherein the crosslinking enhancer has a functionality of at least 2,

wherein wt% is based on the combined weight of the functionalized ethylene and propylene copolymer and the crosslinking enhancer.

10. The composition according to claim 8 or 9, wherein the weight ratio of ethylene to propylene in the functionalized ethylene and propylene copolymer is from 20:80 to 70:30, preferably from 25:75 to 60: 40.

11. The composition according to any one or more of claims 8 to 10, wherein the enthalpy of fusion is preferably from 5J/g to 150J/g, preferably from 10J/g to 120J/g, further preferably from 12J/g to 100J/g, further preferably from 13J/g to 90J/g, further preferably from 14J/g to 80J/g, further preferably from 15J/g to 65J/g, as measured by DSC.

12. The composition according to any one or more of claims 8-11, wherein the functionalized ethylene and propylene copolymer comprises at least one or two types of reversible crosslinks.

13. Thermoplastic composition comprising a functionalized ethylene and propylene copolymer composition according to one or more of claims 8 to 12 and at least one further thermoplastic polymer, preferably selected from polyolefins such as atactic polypropylene, polypropylene homopolymer, heterophasic polypropylene copolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene copolymers, polyesters, polycarbonates, polyester-carbonates, polyurethanes, polyethers, polyetherimides, polyamides, polystyrenes, polyphenylene oxides, polyacrylates, olefin-acrylate copolymers, polysulfones.

14. Use of the composition according to any one or more of claims 8-12 as a shape memory copolymer and/or a self-healing copolymer.

Examples

^{1 13}H and C NMR characterization

By carrying out at 125 deg.C¹³C and¹h NMR analysis to determine ethylene content and percent functionality. The sample was dissolved in deuterated tetrachloroethane (TCE-D2) containing Butylated Hydroxytoluene (BHT) as a stabilizer at 130 ℃. Spectra were recorded in 5mm tubes 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.

High temperature exclusion chromatography (HT-SEC)

Determination of molecular weight (in kg. mol.) by means of high temperature exclusion chromatography^-1Recorded) and PDI, which was carried out at 150 ℃ in a GPC-IR instrument equipped with an IR4 detector and a carbonyl sensor (PolymerChar, valencia, spain column settings: three polymers L associations 13 μm P L gel oxides, 300 × 7.5.5 mm, using 1, 2-dichlorobenzene (o-DCB) as the eluent at a flow rate of 1m L min^-1. The molecular weights and corresponding PDIs were calculated by HT SEC analysis relative to narrow polystyrene standards (meyentz PSS, germany).

Differential Scanning Calorimetry (DSC)

On DSC Q100 from TA Instruments at 5 ℃ min^-1For thermal analysis. At 10 ℃ min^-1After heating to 210 c and 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.