阅读说明：本技术 一种烯烃-烯烃醇共聚物的制备方法 (Preparation method of olefin-olefin alcohol copolymer ) 是由 刘东兵 苏勐轩 高榕 郭子芳 赖菁菁 李昕阳 顾元宁 于 2020-06-05 设计创作，主要内容包括：本发明涉及一种烯烃-烯烃醇共聚物的制备方法及其产物和应用。该烯烃-烯烃醇共聚物的制备方法包括在催化剂和改进剂存在下使烯烃和烯烃醇发生聚合,使用的催化剂为式I所示的二亚胺金属配合物。通过本发明的制备方法可以获得球形和/或类球形聚合物,在工业应用中具有良好的前景。(The invention relates to a preparation method of an olefin-olefin alcohol copolymer, and a product and application thereof. The preparation method of the olefin-olefin alcohol copolymer comprises the step of polymerizing olefin and olefin alcohol in the presence of a catalyst and a modifier, wherein the catalyst is a diimine metal complex shown in a formula I. The preparation method can obtain spherical and/or spheroidal polymers and has good prospect in industrial application.)

1. A process for producing an olefin-olefin alcohol copolymer, which comprises polymerizing an olefin and an olefin alcohol in the presence of a catalyst and an improver to produce the olefin-olefin alcohol copolymer,

wherein the catalyst comprises a main catalyst and an optional cocatalyst, and the main catalyst comprises a diimine metal complex shown as a formula I:

in the formula I, the compound is shown in the specification,

R₁and R₂The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r₅-R₁₀The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent;

m is a group VIII metal;

x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.

2. The method of claim 1, wherein R is₁And R₂Selected from substituted or unsubstituted C1-C20 alkyl and or substituted or unsubstituted C6-C20 aryl, preferably R₁And/or R₂Is a group of formula A:

in the formula A, R¹-R⁵The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r¹-R⁵Optionally forming a ring with each other;

preferably, in formula A, R¹-R⁵The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;

preferably, M is selected from nickel and palladium; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent, more preferably from halogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent.

3. The method of claim 1 or 2, wherein R is₅-R₁₀The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;

preferably, R₅-R₁₀Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

4. A process according to any one of claims 1 to 3, wherein the olefin comprises an olefin having 2 to 16 carbon atoms, preferably the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms, and/or the olefinic alcohol is selected from one or more olefinic alcohols of formula G:

in the formula G, L₁-L₃Each independently selected from H and C with or without substituent₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group;

preferably, the copolymer has a content of structural units derived from the olefin alcohol represented by the formula G of 0.4 to 10.0 mol%;

preferably, L₁And L₂Is H, L₃Is H or C₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group;

more preferably, L₁And L₂Is H, L₃Is H or C₁-C₂₀Alkyl radical, L₄Is C having a pendant group₁-C₂₀An alkylene group;

still more preferably, L₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₁₀An alkylene group;

further preferably, L₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₆An alkylene group.

5. The method of claim 4, wherein L is₁-L₃Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxy; more preferably L₁-L₃Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy;

the side group in L4 is selected from halogen and C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀One or more of alkoxy, said C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl and hydroxyl.

6. A method according to any of claims 1 to 5, characterised in that the modifier comprises a halogenated hydrocarbon, preferably selected from C1-C15 halogenated hydrocarbons, more preferably C1-C10 halogenated hydrocarbons, even more preferably C1-C6 halogenated alkanes.

7. The process according to any one of claims 1 to 6, wherein the polymerization is carried out in the presence of a solvent,

preferably, the solvent is an alkane solvent, preferably one or more of C3-20 alkanes, more preferably C3-C10 alkanes;

preferably, the volume ratio of the solvent to the modifier is (1-5000):1, preferably (1.0-500): 1.

8. A process according to any one of claims 1 to 7, wherein the cocatalyst is selected from organoaluminium compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate;

preferably, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-10)⁷):1, preferably (10-100000) 1, more preferably (100-; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-1000):1, preferably (0.1-500): 1.

9. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 8, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50 mm.

10. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 8 or of the olefin-olefin alcohol copolymer of claim 9 as a polyolefin material.

Technical Field

The invention belongs to the field of preparation of high molecular polymers, and particularly relates to a preparation method of an olefin-olefin alcohol copolymer.

Background

The polyolefin product has the characteristics of stable performance, excellent processing performance, good safety and stability, recycling and the like, so that the polyolefin product is widely applied to the fields of industry and agriculture, medical treatment and health, national defense industry, daily life and the like. However, the main chain of polyethylene is C-C bond and C-H bond with low reactivity, so that the printing property, the adhesive property, the air permeability and the compatibility with other materials of the polyethylene are poor, and the application of the polyethylene is limited. The polar group containing N, O, Si or halogen is introduced into polyolefin molecular chain by chemical synthesis method, which can improve chemical inertia, printing property, wettability and compatibility with other materials, endow new properties which are not possessed by raw materials, and widen application field. The current method commonly used in industry is to directly perform high-pressure radical copolymerization on ethylene and polar monomer to obtain polyethylene containing polar groups, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymer. Although the polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.

Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is one of three barrier resins industrially produced in the world at present, has excellent gas barrier property, processability and biocompatibility, and is widely used for packaging of food and medicines, medical supplies and other products. Since vinyl alcohol cannot exist stably in the form of monomers, the product is usually prepared industrially as a two-step process: first, ethylene and vinyl acetate are polymerized through free radicals to generate ethylene-vinyl acetate (EVA); and the second step of alcoholysis reaction of the copolymer to obtain EVOH. However, a large amount of solvent is needed in the free radical polymerization process, the recovery is difficult, a large amount of alcohol solvent is needed in the alcoholysis process, the final saponification product contains a large amount of impurities such as sodium acetate, methyl acetate and the like, a large amount of water is needed for washing the product, and the energy consumption is high.

Compared with free radical polymerization, coordination polymerization for realizing the copolymerization of olefin isotropic monomers can obtain products with higher molecular weight under a milder condition, can conveniently regulate and control the insertion amount of polar monomers, can regulate the performance of the products in a wider range, has lower cost, and is one of the hotspots in the research field of polyolefin materials. Only a few reports have been made of the use of transition metal complexes to catalyze the copolymerization of ethylene with enol, such as Journal of Applied Polymer Science,2013,129(4): 1820-; ACS Catal, 2017,7(2):1308-1312, wherein a phosphine-nickel sulfonate catalyst (formula b) is adopted to catalyze the copolymerization of ethylene and hydroxyl-substituted norbornene; angewandte Chemie International Edition,2017,56(38): 11604-. However, in the existing reports, although the transition metal complex is adopted to successfully catalyze the copolymerization of the enol of ethylene with different structures, the product is a viscous solid with a random structure, and the product is easy to adhere and scale in polymerization equipment, thereby bringing difficulties to the procedures of further removing the solvent, granulating and the like of the product, and not meeting the requirements of industrial production.

Disclosure of Invention

It is an object of the present invention to overcome the disadvantages of the prior art and to provide a novel process for preparing olefin-olefin alcohol copolymers. Furthermore, the spherical and/or spheroidal polymer can be directly obtained by the method, the polymer has good appearance and good industrial application prospect.

In a first aspect, the present invention provides a process for preparing an olefin-olefin alcohol copolymer, comprising polymerizing an olefin and an olefin alcohol in the presence of a catalyst solvent and an improver to produce the olefin-olefin alcohol copolymer.

According to an embodiment of the invention, the catalyst comprises a procatalyst comprising a diimine metal complex according to formula I:

in the formula I, R₁And R₂The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r₅-R₁₀The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent.

M is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.

According to some embodiments of the invention, R₁And R₂Is selected from C1-C20 alkyl with or without substituent and/or C6-C20 aryl with or without substituent.

According to some embodiments of the invention, R₁And/or R₂Is a group of formula A:

in the formula A, R¹-R⁵The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r¹-R⁵Optionally forming a ring with each other.

According to some embodiments of the invention, R in formula A¹-R⁵The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.

According to some embodiments of the invention, M is selected from nickel and palladium.

According to some embodiments of the invention, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C1-C10 alkoxy, preferably from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.

According to some embodiments of the invention, R₅-R₁₀The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, and with or without substituentC2-C10 alkenyl containing substituent groups, C2-C10 alkynyl containing substituent groups or not, C3-C10 cycloalkyl containing substituent groups or not, C1-C10 alkoxy containing substituent groups or not, C2-C10 alkenyloxy containing substituent groups or not, C2-C10 alkynyloxy containing substituent groups or not, C3-C10 cycloalkoxy containing substituent groups or not, C6-C15 aryl containing substituent groups or not, C7-C15 aralkyl containing substituent groups or not, and C7-C15 alkaryl containing substituent groups or not.

According to some embodiments of the invention, R₅-R₁₀Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

According to some embodiments of the invention, the substituent is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

According to some embodiments of the invention, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3, 3-dimethylbutyl.

According to some embodiments of the invention, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3, 3-dimethylbutoxy.

According to some embodiments of the invention, the halogen is selected from fluorine, chlorine, bromine and iodine.

According to some embodiments of the invention, the alkene alcohol is selected from one or more of the alkene alcohols represented by formula G:

in the formula G, L₁-L₃Each independently selected from H and C with or without substituent₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group.

According to some embodiments of the invention, the copolymer has a content of structural units derived from the alkene alcohol represented by formula G of 0.4 to 10.0 mol%.

According to some embodiments of the invention, in formula G, L₁And L₂Is H.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₃₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₃₀An alkylene group.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₂₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₂₀An alkylene group.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₁₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₁₀An alkylene group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₆An alkylene group.

According to some embodiments of the invention, L₁-L₃Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxyl.

According to some embodiments of the invention, L₁-L₃Wherein the substituent is selected from C1-C6 alkyl,One or more of halogen and C1-C6 alkoxy.

According to some embodiments of the invention, the pendant group in L4 is selected from halogen, C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀One or more of alkoxy, said C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl and hydroxyl.

According to a preferred embodiment of the invention, said L₄The side group in (A) is selected from halogen and C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl, hydroxy substituted C₁-C₂₀Alkyl and alkoxy substituted C₁-C₂₀One or more of alkyl; preferably, the side group is selected from halogen, C₆-C₂₀Aryl radical, C₁-C₁₀Alkyl, hydroxy substituted C₁-C₁₀Alkyl and alkoxy substituted C_1-10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C₁-C₆Alkyl and hydroxy substituted C₁-C₆One or more of alkyl, said C₁-C₆Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.

According to a preferred embodiment of the invention, in formula G, L₁And L₂Is H, L₃Is H or C₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group; said C is₁-C₃₀Alkyl is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxyl.

According to a preferred embodiment of the inventionIn the formula G, L₁And L₂Is H, L₃Is H, C₁-C₁₀Alkyl or halogen substituted C₁-C₁₀Alkyl, preferably L₃Is H or C₁-C₁₀An alkyl group; l is₄Is C having a pendant group₁-C₂₀Alkylene radicals, e.g. L₄Is methylene with side group, ethylene with side group, propylene with side group, butylene with side group, C with side group₅Alkylene, C having pendant groups₆Alkylene, C having pendant groups₇Alkylene, C having pendant groups₈Alkylene, C having pendant groups₉Alkylene, C having pendant groups₁₀Alkylene, C having pendant groups₁₂Alkylene, C having pendant groups₁₄Alkylene, C having pendant groups₁₈Alkylene, C having pendant groups₂₀Alkylene, preferably C, having pendant groups₁-C₁₀An alkylene group.

According to a preferred embodiment of the invention, in formula G, L₁And L₂Is H, L₃Is H or C_1-6An alkyl group; l is₄Is C having a pendant group₁-C₁₀An alkylene group.

In the present invention, the carbon number n of the Cn alkylene group means the number of C's in the linear chain, excluding the number of C's in the pendant group, and is, for example, isopropylidene (-CH)₂-CH(CH₃) -) is referred to herein as C with a pendant group (methyl)₂An alkylene group.

According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include, but are not limited to: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2, 4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 2-methyl-3-buten-ol, 2-methyl-4-penten-2-ol, 2-methyl-4-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-2-ol, and mixtures thereof, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-2-heptene, 2-methyl-2-1-heptene, 2-methyl-2-4-methyl-6-heptene, 2-methyl-4-heptene, 2-1-octene, 2-octene, 2-heptene, 2-octene, 2-one, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1, 2-dihydroxy-7-octene, 2, 6-dimethyl-2, 6-dihydroxy-7-octene, 2, 6-dimethyl-2, 3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.

According to a preferred embodiment of the invention, the cocatalyst is chosen from organoaluminum compounds and/or organoboron compounds.

According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlR_nX¹ _3-nWith an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlR_nX¹ _3-nWherein R is H, C₁-C₂₀Saturated or unsaturated hydrocarbon radicals or C₁-C₂₀Saturated or unsaturated hydrocarbyloxy radicals, preferably C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy radical, C₇-C₂₀Aralkyl or C₆-C₂₀An aryl group; x¹Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride,Ethyl aluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).

According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.

According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5 mmol/L.

According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, and any value therebetween, preferably (0.1-500): 1.

According to preferred embodiments of the present invention, the olefin comprises an olefin having from 2 to 16 carbon atoms, and in some embodiments of the present invention, the olefin comprises ethylene or alpha-olefins having from 3 to 16 carbon atomsAn olefin. In other embodiments of the present invention, the olefin is C₃-C₁₆A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C₂-C₁₀Alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene and octene.

According to a preferred embodiment of the present invention, the concentration of the olefin alcohol monomer represented by the formula G in the reaction system is 0.01 to 6000mmol/L, preferably 0.1 to 1000mmol/L, more preferably 1 to 500mmol/L, and may be, for example, 1mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 90mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400mmol/L, 500mmol/L and any value therebetween.

According to a preferred embodiment of the invention, the modifier comprises a halogenated hydrocarbon, preferably selected from the group consisting of C1-C15 halogenated hydrocarbons, more preferably C1-C10 halogenated hydrocarbons, even more preferably C1-C6 halogenated alkanes.

According to a preferred embodiment of the invention, the improver comprises methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1,1,1, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 2-chloropropane, chloro-n-propane, 1, 3-dichloropropane, 1,1, 2-trichloropropane, 1,1,2,2,3, 3-hexachloropropane, 1,1,1,2,2,3, 3-heptachloropropane, 1-chlorobutane, chloro-tert-butane, 1, 4-dichlorobutane, 1, 2-dichloroisobutane, 1,1, 2-trichloro-2-methylpropane, 1,2,3, 4-tetrachlorobutane, 1-chloropentane, 2-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2, 2-dimethylpropane, 1-chloro-2-methylbutane, 1, 5-dichloropentane, 2, 2-dimethyl-1, 3-dichloropropane, 1,1,1- (trichloromethyl) ethane, tetrachloro-pentanes.

According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent selected from C₃-C₂₀One or more alkanes, preferably selected from C₃-C₁₀Alkanes, for example, may be chosen from butane, isobutane, pentane, hexane, heptane,One or more of octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.

According to a preferred embodiment of the invention, the volume ratio of solvent to modifier used for the polymerization is (1-5000):1, preferably (1.0-500): 1. For example, 1:1, 2:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1, and any value in between, preferably (1.0-500): 1.

According to a preferred embodiment of the present invention, the olefinic alcohol is pre-treated with a dehydroactive hydrogen, preferably with the use of a cocatalyst as described above, to remove hydroxyl active hydrogen from the olefinic alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst during pretreatment is from 10:1 to 1: 10.

According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.

According to a preferred embodiment of the invention, the conditions of the reaction include: the temperature of the reaction is-50 ℃ to 50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process. In the present invention, the "reaction system" is meant to include the totality of solvent, olefin alcohol monomer, catalyst, modifier and optionally chain transfer agent.

The invention also provides an olefin-olefin alcohol copolymer prepared by the preparation method, which comprises spherical and/or spheroidal polymers.

According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0 mm.

According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by the formula G is 0.4 to 30.0 mol%, and for example, may be 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol% and any value therebetween, preferably 0.7 to 10.0 mol%.

According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 30000-500000, preferably 50000-400000.

According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.

In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.

According to still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a polyolefin material.

The process for producing an olefin-olefin alcohol copolymer provided by the present invention uses a modifier. The technical problem to be solved by the invention is to provide a novel preparation method of olefin-olefin alcohol copolymer.

Furthermore, in the preparation method of the olefin-olefin alcohol copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the olefin alcohol monomer for reaction, the catalyst and a proper modifier polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.

Further, compared with the existing industrial process for preparing olefin-olefin alcohol copolymers, the method for preparing olefin-olefin alcohol copolymers provided by the invention omits the step of saponification reaction, and has simpler preparation process.

Symbols such as R used in different formulae or structural formulae herein¹、R²、R³、R⁴、R⁵、R₁-R₁₀、R₅X, M, A, etc., have the same definitions in each general formula or structural formula unless otherwise specified.

In the present invention, examples of the halogen include fluorine, chlorine, bromine, and iodine.

In the present invention, C₁-C₂₀Alkyl is C₁-C₂₀Straight chain alkyl or C₃-C₂₀Branched alkyl groups of (a), including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.

C₃-C₂₀Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

C₆-C₂₀Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.

C₂-C₂₀Alkenyl means C₁-C₂₀Linear alkenyl of (A) or (C)₃-C₂₀Including but not limited to: vinyl, allyl, butenyl.

C₇-C₂₀Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.

C₇-C₂₀Examples of alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

The analytical characterization instrument used in the present invention was as follows:

comonomer content of the polymer (content of structural units derived from the olefin alcohol represented by formula G): by using¹³C NMR spectroscopy was carried out by dissolving a polymer sample in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.

Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the copolymer: measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).

The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). times.2.

Example 1

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 10mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt₃(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 2

A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with N2 gas 3 times. To the polymerization system was charged 500mL of hexane while adding 3.8mg (6. mu. mol) of complex Ni1, 50mL of dichloromethane, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L in hexane), 10mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 3

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 100mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt₃(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 4

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 200mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt₃(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 5

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 400mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt₃(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 6

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was charged to the polymerization system while adding 3.8mg (6. mu. mol) of complex Ni1, 50mL of 1, 2-dichloroethane, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt₃(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 7 (comparative)

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 3.8mg (2.5. mu. mol) of complex Ni1, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L in hexane), 10mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

TABLE 1

As can be seen from Table 1, in the preparation method of the invention, when the catalyst catalyzes the copolymerization of ethylene and enol, the polymerization activity is higher, and the obtained polymer has higher sphericity. By regulating and controlling the polymerization conditions, a copolymerization product with good particle morphology can be prepared.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.