Ligand compound and preparation method thereof, and complex and preparation method and application thereof

Abstract

The invention provides a ligand compound and a preparation method thereof, a complex and a preparation method and application thereof, and belongs to the technical field of polyolefin, the ligand compound has a structure as shown in formula (I) or formula (II): # imgabs 0 # formula (I) and # imgabs 1 # formula (II); b1, b2, b3, R1 and R2 are respectively and independently selected from any one of hydrogen, substituted or unsubstituted alkyl with 1 to 5 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, alkoxy with 1 to 5 carbon atoms, aryl with 6 to 30 carbon atoms and fused ring aryl with 10 to 50 carbon atoms; r1 and R2 are connected to form a ring or are not connected to form a ring; b1, b2, b3, b4 and b5 are respectively and independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl and C1-C5 alkoxy; c1, c2 and c3 are respectively and independently selected from any one of hydrogen, substituted or unsubstituted alkyl with 1 to 5 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, alkoxy with 1 to 5 carbon atoms and phenoxy; r1, R2, R3 and R4 are respectively and independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl, C3-C10 cycloalkyl and substituted phenyl.

Description

Technical Field

[0001] The present invention relates to the technical field of polyolefins, and in particular to a ligand compound and a preparation method thereof, a complex and a preparation method and application thereof. Background Art

[0002] Polyolefin elastomer (POE) is a type of polyolefin elastomer material formed by copolymerization of ethylene and α-olefins (1-octene, 1-butene, etc.). The catalytic system mainly uses a constrained geometry metallocene catalyst (CGC catalyst) for catalysis. Due to the high content of comonomers and low density in the POE molecular chain, the formed polymer chain consists of a crystalline resin phase and an amorphous rubber phase. Therefore, POE has both the high elasticity of rubber and the plasticity and easy processing of thermoplastic resins.

[0003] Polyolefin elastomers are usually prepared by copolymerizing expensive long-chain α-olefins as comonomers with ethylene. These α-olefins are mainly imported, and the CGC catalysts and α-olefins used are relatively expensive, resulting in high production costs. Summary of the invention

[0004] In view of this, in order to at least partially solve the above-mentioned technical problems, the present invention provides ligand compounds and preparation methods, complexes and preparation methods, and applications.

[0005] According to an embodiment of one aspect of the present invention, there is provided a ligand compound having a structure as shown in formula (I) or formula (II):

[0006] Formula (I), Formula (II);

[0007] b 1 , b 2 , b 3 , R 1 , R 2 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Alkoxy, C 6 ~C 30 Aryl, C 10 ~C 50 Any one of the fused ring aromatic groups; R 1 , R 2 Connected into a ring or not connected into a ring, in R 1 , R 2When connected into a ring, R 1 , R 2 Connect to form C 10 ~C 50 Condensed ring aromatic group; b 4 , b 5 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of the alkoxy groups; c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of alkoxy and phenoxy; R 3 , R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 3 ~C 10 Any one of cycloalkyl and substituted phenyl, wherein the substituent of the substituted phenyl includes C 1 ~C 5 Alkyl; in the case of a substituent on a substituted or unsubstituted group, the substituent is selected from halogen, C 1 ~C 5 Alkyl, C 6 ~C 12 Aryl, C 3 -C 30 Any of the heteroaryl groups.

[0008] According to an embodiment of the present invention, b 1 , b 2 , b 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, in C 1 ~C 5 When there is a substituent on the alkyl group, the substituent is selected from C 6 ~C 12 Aryl; R 1 , R 2are independently selected from any one of hydrogen, methyl, ethyl, isopropyl and tert-butyl; R 1 , R 2 Connected into a ring or not connected into a ring, in R 1 , R 2 When connected into a ring, R 1 , R 2 Connected to form any one of naphthyl, fluorenyl, acenaphthenyl, and phenanthryl; b 4 , b 5 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl and methoxy; c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Any of alkyl and phenoxy groups, in C 1 ~C 5 When the alkyl group has a substituent, there are 1 to 3 substituents, each of which is independently selected from C 6 ~C 12 Any one of aryl, thiophene, furan, and selenophene; R 3 , R 4 Each is independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexane and substituted phenyl.

[0009] According to an embodiment of the present invention, the ligand compound has the formula (I 1 )~Formula (I 6 ), formula (II 1 )~Formula (II 3 ) in any of the following structures:

[0010] Formula (I 1 )、 Formula (I 2 )、

[0011] Formula (I 3 )、 Formula (I 4 )、

[0012] Formula (I 5 )、 Formula (I 6 )、

[0013] Formula (II 1 )、 Formula (II 2 )、

[0014] Formula (II 3 ).

[0015] According to another embodiment of the present invention, a method for preparing the above-mentioned ligand compound is provided, the method comprising: treating a compound represented by formula (A) , the compound represented by formula (B) , the compound represented by formula (C) Carry out condensation reaction to obtain the ligand compound represented by formula (I); or the compound represented by formula (D) , the compound represented by formula (E) A condensation reaction is carried out to obtain a ligand compound represented by formula (II).

[0016] According to an embodiment of the present invention, the catalyst used in the condensation reaction includes p-toluenesulfonic acid, the temperature of the condensation reaction is 110-130° C., and the reaction time is 11-13 hours.

[0017] According to another embodiment of the present invention, there is provided a complex having a structure as shown in formula (III) or formula (IV):

[0018] Formula (III), Formula (IV);

[0019] Among them, b 1 , b 2 , b 3 , R 1 , R 2 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Alkoxy, C 6 ~C 30 Aryl, C 10 ~C 50 Any one of the fused ring aromatic groups; R 1 , R 2 Connected into a ring or not connected into a ring, in R 1 , R 2 When connected into a ring, R 1 , R 2 Connect to form C 10 ~C 50 Condensed ring aromatic group; b 4 , b 5are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of the alkoxy groups; c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of alkoxy and phenoxy; R 3 , R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 3 ~C 10 Any one of cycloalkyl and substituted phenyl, wherein the substituents of the substituted phenyl include C 1 ~C 5 Alkyl; in the case of a substituent on a substituted or unsubstituted group, the substituent is selected from halogen, C 1 ~C 5 Alkyl, C 6 ~C 12 Aryl, C 3 -C 30 any one of heteroaryl groups; M is selected from any one of Ni, Pd, Fe, and Co; X and Y are independently selected from any one of halogen, methyl, phenyl, and acetylacetonate.

[0020] According to another embodiment of the present invention, there is provided a method for preparing the above-mentioned complex, the method comprising: subjecting a ligand compound having a structure as shown in formula (I) or formula (II) to a coordination reaction with a divalent metal compound to obtain a complex having a structure as shown in formula (III) or formula (IV); the divalent metal compound comprises at least one of ethylene glycol dimethyl ether nickel bromide, nickel chloride, nickel iodide, allyl nickel chloride, triphenylphosphine nickel chloride, palladium chloride, and alkyl palladium chloride.

[0021] According to another embodiment of the present invention, there is provided a use of the complex as described above as a late transition metal catalyst in a solution polymerization process of a polyolefin elastomer.

[0022] According to an embodiment of the present invention, the solution polymerization process of polyolefin elastomer uses ethylene as the only olefin monomer raw material.

[0023] According to an embodiment of the present invention, a solution polymerization process of a polyolefin elastomer comprises: adding a co-catalyst, a complex and an ethylene monomer into an organic solvent to allow the ethylene monomer to undergo a homopolymerization reaction; the co-catalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, sesquiethylaluminum, methylaluminoxane, modified methylaluminoxane, triphenylcarbon tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0024] According to an embodiment of the present invention, the present invention uses diimine or pyridine imine as a skeleton, and at one end of the diimine skeleton or the pyridine imine skeleton, that is, the ortho-substituent of the N-aryl group uses a structure with a large steric hindrance, which has a strong π conjugation effect, and a group with a small steric hindrance is connected to the other end of the diimine skeleton or the pyridine imine skeleton, so that the ligand compound has a high thermal stability when coordinated to form a bond with a divalent metal. By setting this asymmetric structure, it is helpful to improve the effective coordination of olefin monomers and promote a certain degree of chain walking of olefin monomers, thereby helping to prepare a polyolefin elastomer with a suitable degree of branching. DETAILED DESCRIPTION

[0025] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0026] In the case of using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, or C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0027] In the present invention, the term "substituted or unsubstituted" group may be substituted with one substituent or multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the present invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0028] In the present invention, “each independently” means that when there are multiple subjects, they may be the same as or different from each other.

[0029] In the present invention, the expression of chemical elements, unless otherwise specified, generally includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen (H)" also includes the concepts of 1H (protium or H) and 2H (deuterium or D) with the same chemical properties; carbon (C) includes 12C, 13C, etc., which will not be repeated.

[0030] In the present invention, C a ~C b The expression "a" means that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent.

[0031] In the present invention, the term "alkyl" may include a branched or straight chain saturated aliphatic monovalent hydrocarbon group having a specified number of carbon atoms. 1 ~C 20 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups.

[0032] The polyolefin elastomers (POE) commonly used in the relevant technology are mostly formed by copolymerization of ethylene and α-olefin. POE has the following advantages: narrow molecular weight distribution, high α-olefin content, low density and crystallinity, and exhibits excellent mechanical properties, such as high elongation at break, high elasticity, excellent impact resistance and low temperature resistance. Containing a non-polar saturated single-bond chain structure, no vulcanization is required, so that POE has the characteristics of heat resistance, heat-oxidative aging resistance, UV resistance, water vapor resistance and corrosion resistance. It has both the plasticity of the crystalline resin phase and the high elasticity of the amorphous rubber phase, can undergo plastic flow, has excellent processing rheological properties, is easy to extrude or injection molding, and is not prone to flexural deformation. It has excellent high transparency, toughness and compatibility, and can be widely used in toughening and modification of olefin polymers.

[0033] In the preparation process of POE, the production cost is high due to the use of relatively expensive α-olefins and metallocene catalysts.

[0034] It is well known to those skilled in the art that the olefin polymerization process mainly includes three steps: chain growth, chain transfer and chain walking. When the complex containing asymmetric α-diimine proposed in the present invention is used as a metal catalyst, ethylene coordinates with the metal center of the metal catalyst and inserts into the metal-alkyl bond to form chain growth; β-H elimination occurs during the ethylene insertion process, and the metal center vacancy of the metal catalyst coordinates with new ethylene to form chain transfer; after β-H elimination occurs, ethylene flips 180° and coordinates and inserts with the metal center of the metal catalyst again to form chain walking.

[0035] In the related art, when a commonly used asymmetric α-diimine complex is used as a catalyst, when catalyzing ethylene homopolymerization, polyethylene is usually catalyzed to form, that is, a resin phase mainly presenting a crystalline state. However, when the complex of the present invention catalyzes ethylene homopolymerization, the chain running of the ethylene monomer is adjusted, so that the prepared polyolefin elastomer can have both the high elasticity of rubber and the plasticity of thermoplastic resin.

[0036] Specifically, according to an embodiment of one aspect of the present invention, there is provided a ligand compound having a structure as shown in formula (I) or formula (II):

[0037] Formula (I), Formula (II);

[0038] Among them, b 1 , b 2 , b 3 , R 1 , R 2 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Alkoxy, C 6 ~C 30 Aryl, C 10 ~C 50 Any one of the fused ring aromatic groups; R 1 , R 2 Connected into a ring or not connected into a ring, in R 1 , R 2 When connected into a ring, R 1 , R 2 Connect to form C 10 ~C 50 Condensed ring aromatic group; b 4 , b 5 are independently selected from hydrogen, substituted or unsubstituted C1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of the alkoxy groups; c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of alkoxy and phenoxy; R 3 , R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 3 ~C 10 Any one of cycloalkyl and substituted phenyl, wherein the substituent of the substituted phenyl includes C 1 ~C 5 Alkyl; in the case of a substituent on a substituted or unsubstituted group, the substituent is selected from halogen, C 1 ~C 5 Alkyl, C 6 ~C 12 Aryl, C 3 -C 30 Any of the heteroaryl groups.

[0039] The ligand compound shown in formula (I) uses α-diimine as the main skeleton, and the ortho-substituent of the N-aryl at one end of the diimine skeleton uses a diphenylmethyl group with a large steric hindrance, which has a strong conjugation effect, can enhance the electron donor ability of the ligand compound, and is helpful to adjust the electron cloud density of the metal center of the subsequent preparation of the complex. In the subsequent catalytic polymerization of ethylene, it is helpful to improve the selectivity and activity of the polymerization reaction and improve the thermal stability of the prepared polyolefin elastomer.

[0040] The ortho-substituent of the N-aryl group at the other end of the diimide skeleton uses a group with less steric hindrance to form an asymmetric structure. Such an asymmetric structure promotes the effective coordination of the olefin monomers and the chain walking of the olefin monomers within a certain range during the reaction, which helps to prepare a polyolefin elastomer with a required degree of branching, so that the polyolefin elastomer has both the high elasticity of rubber and the plasticity of thermoplastic resin.

[0041] The ligand compound shown in formula (II) constructs an asymmetric structure on both sides of the main skeleton of pyridine imine by a mechanism similar to that of the diimine skeleton, which promotes the chain movement of the olefin monomer within a certain range during the polymerization reaction. It also helps to prepare a polyolefin elastomer with a moderate degree of branching, so that the polyolefin elastomer has both the high elasticity of rubber and the plasticity of thermoplastic resin.

[0042] Since the present invention uses a ligand compound represented by formula (I) or formula (II), the use of expensive α-olefins and metallocene catalysts is avoided, which can significantly reduce production costs and improve the thermal stability of the prepared polyolefin elastomer, which is conducive to industrial application.

[0043] It should be noted that chain walking is a unique process in late transition metal-catalyzed ethylene polymerization. The branch type, density, topology, branch stereochemistry, etc. of the prepared polyolefin elastomer can be controlled by adjusting the structure of the ligand compound. The catalyst combines with the main chain molecule of ethylene to form an α-olefin molecule through the elimination reaction of β-H. The molecule rotates through the chain, and the metal active center chain walks to the second carbon position, repeats to the third carbon position, and then gradually walks to the nth carbon position. By adjusting the process parameters, chain transfer or termination is performed to prepare a polyolefin elastomer with a certain degree of branching.

[0044] Preferably, b 1 , b 2 , b 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, in C 1 ~C 5 When there is a substituent on the alkyl group, the substituent is selected from C 6 ~C 12 Aryl; More preferably, b 1 , b 2 are independently selected from hydrogen, methyl, ethyl, isopropyl, and tert-butyl, wherein methyl, ethyl, isopropyl, and tert-butyl are substituted or unsubstituted, 1 , b 2 , b 3 When substituted, the substituent is selected from at least one of phenyl, biphenyl, terphenyl, diphenylmethyl, naphthyl, fluorene, and spirofluorene. 1 , b 2 Can be the same or different. 3 Selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl. 3 Can be used with b 1 , b 2 At least one of them is the same as b 1, b 2 Are different.

[0045] Preferably, R 1 , R 2 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl and tert-butyl; 1 , R 2 When connected into a ring, R 1 , R 2 Connected to form any one of naphthyl, fluorenyl, acenaphthenyl, and phenanthryl, more preferably acenaphthenyl; b 4 , b 5 Each is independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl and methoxy.

[0046] In the relevant experiments, it was found that when the groups in formula (I) were selected from the above ranges, it was more conducive to the insertion of olefin monomers to prepare a polyolefin elastomer with a certain degree of branching. Compared with the polyolefin elastomer in the related art, the polyolefin elastomer prepared by the present invention has higher toughness and mechanical strength.

[0047] Preferably, c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Any of alkyl and phenoxy groups, in C 1 ~C 5 When the alkyl group has a substituent, there are 1 to 3 substituents, each of which is independently selected from C 6 ~C 12 Any one of aryl, thiophene, furan, selenophene; more preferably, c 1 、c 3 are independently selected from substituted C 1 ~C 5 Alkyl, phenoxy, C 1 ~C 5 There are two substituents on the alkyl group, each of which is independently selected from any one of benzyl, thiophene, and furan. 1 、c 3 Can be the same or different. 2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl. 2 Can be used with c 1 、c 3 At least one of them is the same as c 1 、c 3 Are different.

[0048] More preferably, c 1 、c3 are independently 2 methyl groups substituted with benzyl, 2 methyl groups substituted with phenyl, 2 methyl groups substituted with thiophene, and phenoxy; c 2 It is methyl.

[0049] Preferably, R 3 , R 4 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, and substituted phenyl; more preferably, R 3 is methyl, R 4 It is tert-butyl, cyclohexane, and 1,3-diisopropyl-5-methylbenzene.

[0050] Using pyridine imine as the main skeleton, similar to the mechanism of α-diimine, a ring structure with large steric hindrance is constructed at the ortho position of the N-aryl group on the side away from the pyridine group on the pyridine imine, which has a large conjugation effect, helps to improve the selectivity and activity of the polymerization reaction, and improves the thermal stability of the prepared polyolefin elastomer. The substituent connected to the side close to the pyridine group has a small steric hindrance. When the complex is formed to catalyze ethylene homopolymerization, the olefin monomer is prompted to insert into the metal center and a certain range of chain walking is carried out, which helps to prepare a polyolefin elastomer with a required degree of branching.

[0051] According to an embodiment of the present invention, the ligand compound has the formula (I 1 )~Formula (I 6 ), formula (II 1 )~Formula (II 3 ) in any of the following structures:

[0052] Formula (I 1 )、 Formula (I 2 )、

[0053] Formula (I 3 )、 Formula (I 4 )、

[0054] Formula (I 5 )、 Formula (I 6 )、

[0055] Formula (II 1 )、 Formula (II 2 )、

[0056] Formula (II 3 ).

[0057] In the process of conducting relevant experiments of the present invention, it was found that the above-mentioned ligand compound, after being subsequently prepared into a complex, can catalyze ethylene homopolymerization into a complex with a good degree of branching. When applied to ethylene homopolymerization, the prepared polyolefin elastomer has better performance.

[0058] According to another embodiment of the present invention, there is provided a method for preparing the above-mentioned ligand compound, comprising: treating a compound represented by formula (A) , the compound represented by formula (B) , the compound represented by formula (C) Carry out condensation reaction to obtain the ligand compound shown in formula (I). Or the compound shown in formula (D) , the compound represented by formula (E) A condensation reaction is carried out to obtain a ligand compound represented by formula (II).

[0059] According to an embodiment of the present invention, a diimine ligand compound or a pyridine imine ligand compound with an asymmetric structure is prepared by condensing several monomers, which helps to promote the movement of the ethylene chain when the complex is subsequently formed to catalyze ethylene homopolymerization, thereby preparing a polyolefin elastomer.

[0060] In some embodiments, the catalyst used in the condensation reaction includes p-toluenesulfonic acid, the condensation reaction temperature is 110-130°C, for example, 110°C, 120°C or 130°C, and the reaction time is 11-13h, for example, 11h, 12h or 13h.

[0061] In one specific embodiment, the preparation process of the compound represented by formula (I) is as follows: the compound represented by formula (A) , the compound represented by formula (B) , the compound represented by formula (C) The mixture is mixed in a 100 mL round-bottom flask, p-toluenesulfonic acid and the first solvent are added, and then placed in an oil bath at 120°C for condensation reaction (water separation reaction). The water separation reaction can be understood as separation of solvent and water, and water is insoluble in the organic solvent to achieve stratification. After the reaction is completed, the first solvent is vacuum concentrated, and the obtained crude product is separated by column chromatography, and the separation column is a neutral alumina column (eluent V (ethyl acetate) / V (polyethylene) = 1 / 50) to obtain a diimine ligand compound (shown in formula (I)).

[0062] Preferably, the molar ratio of the three compounds is 1:1:1, for example, each of them can be 5 mmol. The first solvent can be toluene, and the amount of toluene used is 50 mL.

[0063] In one specific embodiment, the preparation process of the compound represented by formula (II) is as follows: the compound represented by formula (D) , the compound represented by formula (E) The mixture was mixed in a 100 mL round-bottom flask, p-toluenesulfonic acid and the first solvent were added, and then placed in an oil bath at 120° C. for condensation reaction (water separation reaction). After the reaction was completed, the first solvent was vacuum concentrated, and the obtained crude product was separated by column chromatography, and the separation column was a neutral alumina column (eluent V (ethyl acetate) / V (polyethylene) = 1 / 50) to obtain a pyridine imine ligand compound (shown in formula (II)).

[0064] Preferably, the molar ratio of the two compounds is 1:1, for example, both can be 5 mmol. The first solvent can be toluene, and the amount of toluene is 50 mL.

[0065] According to another embodiment of the present invention, there is provided a complex having a structure as shown in formula (III) or formula (IV):

[0066] Formula (III), Formula (IV);

[0067] Among them, b 1 , b 2 , b 3 , R 1 , R 2 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Alkoxy, C 6 ~C 30 Aryl, C 10 ~C 50 Any one of the fused ring aromatic groups; R 1 , R 2 Connected into a ring or not connected into a ring, in R 1 , R 2 When connected into a ring, R 1 , R 2 Connect to form C 10 ~C 50 Condensed ring aromatic group; b 4 , b 5 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of the alkoxy groups; c 1 、c 2 、c 3 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 5 Any of alkoxy and phenoxy; R 3 , R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 ~C 5 Alkyl, C 3 ~C 10 Any one of cycloalkyl and substituted phenyl, wherein the substituent of the substituted phenyl includes C 1 ~C 5 Alkyl; in the case of a substituent on a substituted or unsubstituted group, the substituent is selected from halogen, C 1 ~C 5 Alkyl, C 6 ~C 12 Aryl, C 3 -C 30 Any of the heteroaryl groups.

[0068] M is selected from any one of Ni, Pd, Fe, and Co, preferably Ni or Pd. X and Y are independently selected from any one of halogen, methyl, phenyl, and acetylacetonato, and X and Y may be the same or different, preferably chlorine, bromine, and methyl.

[0069] It should be noted that the b 1 , b 2 , b 3 , R 1 , R 2 , R 3 , R 4 、c 1 、c 2 、c 3 The preferred group range is the same as that of the ligand compound and will not be repeated here.

[0070] According to the embodiments of the present invention, the insertion position of the metal coordination center in the formed complex has a good regulating effect on the catalytic polymerization of olefin monomers. By constructing an adaptive steric space, the position space of the metal insertion can be relatively constrained, thereby constraining the chain walking reaction within a certain spatial range of the metal group, further improving the selectivity and yield of the reaction, preventing the occurrence of unnecessary branch reactions, improving the controllability of the reaction, and facilitating the preparation of a polyolefin elastomer with a certain degree of branching.

[0071] According to an embodiment of the present invention, the complex has the formula (III 1 )~Formula (III 6 ), Formula (IV 1 )~Formula (IV 3 ) in any of the following structures:

[0072] Formula (III 1 )、 Formula (III 2 )、

[0073] Formula (III 3 )、 Formula (III 4 )、

[0074] Formula (III 5 )、 Formula (III 6 )、

[0075] Formula (IV 1 )、 Formula (IV 2 )、

[0076] Formula (IV 3 ).

[0077] According to an embodiment of the present invention, the preparation process of the above-mentioned complex is relatively simple, and when catalyzing ethylene homopolymerization, it can improve the catalytic activity of the metal center, improve the thermal stability of the product, and enable the product to maintain a certain degree of branching, thereby having both elasticity and plasticity.

[0078] According to another embodiment of the present invention, there is provided a method for preparing the above-mentioned complex, comprising: subjecting a ligand compound having a structure as shown in formula (I) or formula (II) to a coordination reaction with a divalent metal compound to obtain a complex having a structure as shown in formula (III) or formula (IV); wherein the divalent metal compound comprises at least one of ethylene glycol dimethyl ether nickel bromide, nickel chloride, nickel iodide, allyl nickel chloride, triphenylphosphine nickel chloride, palladium chloride, and alkyl palladium chloride, wherein the alkyl palladium chloride may be methyl palladium chloride, ethyl palladium chloride, or the like.

[0079] In one specific embodiment, a ligand compound having a structure as shown in formula (I) or formula (II) and a divalent metal compound are mixed in a 100 mL Shrek bottle in a glove box, and a second solvent is added to react with the mixture. After the reaction is completed, the mixture is vacuum concentrated, and then recrystallized using anhydrous n-hexane. After filtration, the mixture is washed with n-hexane to obtain a complex having a structure as shown in formula (III) or formula (IV).

[0080] Preferably, the conditions for the coordination reaction are that the molar ratio of the ligand compound to the divalent metal compound is 1:1, the second solvent is anhydrous dichloromethane, the reaction temperature is room temperature, and the reaction time is 6 hours.

[0081] According to another embodiment of the present invention, there is provided a use of the complex as described above as a late transition metal catalyst in a solution polymerization process of a polyolefin elastomer.

[0082] The use of the above-mentioned complex can generate a metal center with high activity, which can effectively activate olefin monomers (such as ethylene, α-olefins, etc.), promote the insertion of olefin monomers into metal-carbon bonds for chain growth, and thus achieve polymerization. The asymmetric diimine ligand skeleton or pyridine imine skeleton of the present invention can affect the stereoselectivity of its metal catalyst, help to regulate the microstructure of the generated polyolefin chain, such as the regularity and sequence distribution of the stereostructure, thereby regulating its branching degree, so that the prepared polyolefin elastomer has both elasticity and plasticity.

[0083] The α-olefin may include, for example, one or more of propylene, 1-butene, 1-hexene, 1-octene, methyl methacrylate, isobutyl methacrylate, etc., which may be used in combination.

[0084] According to an embodiment of the present invention, the solution polymerization process of polyolefin elastomer uses ethylene as the sole olefin monomer raw material. The complex provided by the present invention can use ethylene as the sole olefin monomer raw material, without using α-olefin as a comonomer, and produce vinyl polyolefin elastomer through solution polymerization. The complex has a high abundance, avoids the use of metallocene catalysts and α-olefins, and significantly reduces production costs. The prepared vinyl polyolefin elastomer has stable quality and a wide range of applications, meeting the needs of photovoltaics, automobiles, toughening and strengthening, and other fields.

[0085] According to an embodiment of the present invention, the solution polymerization process of the polyolefin elastomer includes: adding a co-catalyst, a complex and an ethylene monomer into an organic solvent to allow the ethylene monomer to undergo a homopolymerization reaction; the co-catalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum, methylaluminoxane, modified methylaluminoxane, triphenylcarbon tetrakis (pentafluorophenyl) borate, and N,N-dimethylaniline tetrakis (pentafluorophenyl) borate. The co-catalyst is used in combination with the corresponding complex as needed, and since this is not the focus of the present invention, it will not be described one by one here.

[0086] The organic solvent is C 5 -C 30 At least one of an alkane or an isoalkane, an alkyl-substituted cyclohexane, benzene or a homologue of benzene, dichloromethane or a halogenated alkane and a mixture of an alkane (containing a halogenated alkane or benzene). Preferably cyclopentane, toluene, heptane and a mixture thereof, more preferably heptane and cyclohexane.

[0087] The specific structure of the complex of the present invention allows ethylene to form a vinyl polyolefin elastomer with a specific structure during the solution polymerization process, avoiding the use of expensive α-olefins and metallocene catalysts. Compared with the existing metallocene catalytic system, the production cost and unit energy consumption are significantly reduced. The ortho position of the aniline on one side of the complex of the asymmetric α-diimine skeleton and / or pyridine imine skeleton of the present invention has a large steric hindrance, so that the higher the thermal stability of the complex, the electron-donating group at the para position (for example, when it is a methyl or methoxy group) can further increase the thermal stability of the complex, and the combined effect further improves the stability of catalyzing ethylene homopolymerization. The small ortho steric hindrance on the other side of the complex mainly acts on the ethylene monomer for effective coordination, promotes a certain degree of chain walking of the ethylene monomer, and then can prepare a vinyl polyolefin elastomer.

[0088] Furthermore, the reaction conditions of the solution polymerization process are: polymerization temperature of 30~120°C, pressure of 0~10MPa, molar ratio of aluminum of the co-catalyst and metal of the complex of (0~5000):1, reaction residence time of 0~3h, and ethylene monomer solubility of 4~50%.

[0089] The solution polymerization process of the present invention can be equipped with three continuous polymerization reactors as required, and the three polymerization reactors include a first reactor, a second reactor, and a third reactor, which are connected in series in sequence.

[0090] The solution polymerization process of the present invention also includes: wet deashing and devolatilization of the obtained polyolefin glue solution in sequence. Specifically, the glue solution obtained by three polymerization reactors is transported to a flash tank for ethylene monomer and solvent recovery, and then condensed and compressed to purify, and the concentration of the glue solution is controlled to be 20-60%, and then the glue solution is transferred to a steam stripping washing kettle, and the solvent in the glue particles is recovered after three-stage steam stripping washing, and then filtered, dehydrated, dried, and then packaged to obtain a vinyl polyolefin elastomer finished product. The process of the present invention is conducive to the preparation of low-cost, low-material consumption, low-ash, low-volatile high-performance vinyl polyolefin elastomers, and the vinyl polyolefin elastomers have broad application prospects in the fields of photovoltaics, automobiles, and material toughening and reinforcement.

[0091] In one embodiment, the solution polymerization process may include the following steps:

[0092] Raw material pretreatment:

[0093] The solvent (recovered or purchased) in the storage tank is refined through the refining unit to remove impurities. Ethylene or other α-olefins purchased from outside are refined and impurities removed to prepare polymerization-grade monomers. The main catalyst (i.e., complex) and co-catalyst are treated separately to reduce the concentration and used for polymerization.

[0094] Polymerization reaction:

[0095] The mixed co-catalyst is mixed with the solvent, and then mixed with the main catalyst, and quantitatively transferred to the first reactor by a metering pump. The polymerization reaction temperature is controlled at 30-120°C, the reaction pressure is controlled at 0-10MPa, the molar ratio of aluminum in the reaction co-catalyst and the metal (M) in the main catalyst is Al:M=(0-5000):1, the solubility of olefin monomer is controlled at 4%-50%, and the reaction residence time is controlled at 0-3h.

[0096] After passing through the first reactor, the reactor glue is continuously transferred to the second reactor, the polymerization reaction temperature is controlled at 30-120°C, the reaction pressure is controlled at 0-10MPa, the reaction Al:M=(0-5000):1, the reaction monomer solubility is controlled at 4%-50%, and the reaction residence time is controlled at 0-3h.

[0097] After passing through the second reactor, the reactor glue is continuously transferred to the third reactor, the polymerization reaction temperature is controlled at 30-120°C, the reaction pressure is controlled at 0-10MPa, the reaction Al:M=(0-5000):1, the reaction monomer solubility is controlled at 4%-50%, and the reaction residence time is controlled at 0-3h.

[0098] Post-processing process:

[0099] The gum liquid from the third reactor is transported to the flash tank for olefin monomer and solvent recovery. The recovered solvent is transferred to the solvent recovery tank. The recovered olefin monomer is condensed, compressed and purified, and then transferred to the ethylene recovery tank for standby use. The concentration of the gum liquid is controlled at 20%-60%.

[0100] The rubber liquid is transferred to the steam stripping washing kettle, and then washed by steam stripping at 3 levels, with the temperature controlled at 90-150℃ and the pressure controlled at 0-2MPa. The main purpose is to recover the solvent in the rubber particles. The washed rubber particles are transferred to the filtration unit after cooling and washing, and then squeezed and dehydrated. After dehydration, the rubber particles are dried and then automatically packaged.

[0101] The process of three-stage stripping washing is as follows: the glue liquid after flashing passes through the first stripping washing kettle of the glue particle pump, the flashing temperature is 100-120℃, and low-pressure steam is used for flashing. After the glue liquid is flashed and washed in the kettle, it becomes small glue particles, and a part of the solvent and ash are removed; the glue liquid in the first stripping washing kettle is transferred to the second stripping washing kettle by the glue particle pump, the flashing temperature is 100-120℃, and the glue particles are stripped and washed again, the solvent is further recovered, and the ash content in the glue particles is reduced; the glue liquid in the second stripping washing kettle is transferred to the third stripping washing kettle by the glue particle pump, the flashing temperature is 100-120℃, and the glue particles are stripped and washed for the third time, the solvent is further recovered, and the ash content in the glue particles is reduced. The operation is continuously connected in series, and after multiple stages of series stripping, the organic components and ash content of the glue liquid are significantly reduced.

[0102] In the polymerization reaction, the co-catalyst is fed into the solvent, the catalyst and the ethylene. The co-catalyst and the solvent oil molecules are mixed in a certain proportion through a static mixer. The mixed liquid and a certain amount of the prepared catalyst solution are again passed through the static mixer into the loop reactor to react with the ethylene in the reactor to prepare a polyolefin elastomer.

[0103] The three-stage stripping washing is a three-kettle series operation. The main purpose of each stripping washing kettle is to reduce the volatile matter in the rubber particles, recover the solvent, and reduce production costs. The filtration unit can use a crawler filtration device. After the solvent oil is recovered by the stripping washing kettle, the rubber particles without oil pass through the filtration unit and enter the circulating water cooling system for cooling treatment. The temperature is controlled at 30-50°C, and the rubber particles are dehydrated again through the filtration unit. Extrusion dehydration, for example, can be the rubber particles after dehydration, enter the extruder, and then be extruded and dehydrated again. The dehydrated rubber particles are dried under hot air and then enter the automatic packaging system for packaging. Polyolefin elastomer particles can achieve ultra-low residual volatile content, which can reach ≤20ppm under optimal conditions.

[0104] The performance indicators of the prepared polyolefin elastomer particles are shown in Table 1 below:

[0105] Table 1 Relevant performance parameters of E-POE elastomer

[0106]

[0107] It should be noted that the ash content of less than 20 ppm in Table 1 above refers to the conditions under better conditions. Under normal conditions, the ash content can reach less than 30 ppm. Furthermore, under better conditions, the degree of branching can reach 60-80.

[0108] The purpose of the present invention is to provide a method, process and application of preparing polyolefin elastomer with a late transition metal catalyst, wherein the late transition metal catalyst prepared by the present invention is used, ethylene is used as a polymerization monomer, and vinyl polyolefin elastomer is prepared by solution polymerization. Three reaction kettles are connected in series for continuous reaction to prepare the vinyl polyolefin elastomer, and the reaction operation is simple, the stability is good, and the energy consumption is low. Through a water-washing catalytic unit and a water-washing devolatilization unit, the inorganic ash content and organic volatile content of the vinyl polyolefin elastomer are significantly reduced, and the mechanical properties of the vinyl polyolefin elastomer are significantly improved.

[0109] The present invention is further described below by way of examples. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive explanation of embodiments of the present invention. However, it is apparent that one or more embodiments may be implemented without these specific details. Moreover, in the absence of conflict, the details in the following embodiments may be combined arbitrarily into other feasible embodiments.

[0110] It should be noted that the following examples illustrate the specific content of the present invention, the data provided include the synthesis of the part, the synthesis of the metal compound, the method for ethylene polymerization or copolymerization, wherein the synthesis of the complex, the polymerization process is all carried out under anhydrous and oxygen-free conditions, all sensitive substances are stored in a glove box, all solvents are strictly dried and dehydrated, and ethylene gas is purified by dehydration and deoxygenation columns. Without special instructions, all raw materials are directly used after being bought. The method used in the following examples, such as column chromatography, etc., is a method well known in the art, and can be carried out by the description of textbooks or relevant literature, and will not be repeated.

[0111] The degree of branching of the embodiment of the present invention is tested by high temperature nuclear magnetic resonance, the reagent is deuterated tetrachloroethane, and the value represents the number of branches in 1000 carbons; the volatile matter is tested according to GB / T24131.2-2017, and the ash is tested according to GB / T9345.1-2008; the hardness is tested according to GB / T2411-2008; the melt index is tested according to GB / T3682.1-2018, the temperature is 190°C, and the load is 2.16kg; the weight average molecular weight M wThe molecular weight distribution PDI is tested according to SN / T4183-2015; the density is tested according to GB / T1033.1-2008, the volume resistivity is tested according to GB / T31838.2-2019, and the transmittance is tested according to GB / T2410-2008.

[0112] Embodiment 1:

[0113] Preparation process of polyolefin elastomer particles (E-POE) 1:

[0114] Raw material preparation: the co-catalyst is diethylaluminum chloride, the main catalyst is formula (III 1 ), X=Y is Br, M is Ni, the solvent in the solvent tank is cyclohexane, and ethylene is polymerization grade ethylene.

[0115] Formula (III 1 )

[0116] The preparation process of the main catalyst is as follows: weigh the ligand (1 mmol) of formula (I1) and ethylene glycol dimethyl ether nickel bromide (1 mmol) in a 100 mL Shrek bottle in a glove box, add 30 mL of anhydrous dichloromethane and react at room temperature for 6 hours. After the reaction is completed, vacuum concentrate, add anhydrous n-hexane for recrystallization, filter and wash with n-hexane to obtain formula (III 1 ) is a catalyst with the structure shown in FIG.

[0117] Polymerization reaction: cyclohexane and diethylaluminum chloride are mixed, and then mixed with the main catalyst and put into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 50°C, the pressure is 2.5MPa, the ethylene flow rate is 12.5kg / h, the residence time is 1.5h, the catalyst single reactor concentration is 3mg / L, and the molar ratio of diethylaluminum chloride to the main catalyst is 750 to obtain a reaction gel.

[0118] Post-processing process: The reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent. The flash temperature is controlled at 110℃, the pressure is controlled at 0.05MPa, and the glue liquid concentration is controlled at 30%. The glue liquid is transferred to a multi-stage series drying tower and the solvent is recovered through three-stage stripping drying. The stripping temperature is controlled at 115℃ and the pressure is controlled at 0.06MPa.

[0119] The rubber liquid dried by three-stage stripping passes through an automatic filtering device, then washed with water to cool down, the temperature is controlled at 35°C, filtered again, and enters the extrusion equipment for dehydration. After extrusion dehydration, it is dried at 90°C. The water content of the rubber particles is less than 0.15%. The rubber particles enter the screw extruder, are screw extruded and granulated, the screw speed is 50r / min, the temperature is controlled at 120°C, and then automatically packaged to prepare E-POE1.

[0120] Embodiment 2:

[0121] Preparation process of E-POE2:

[0122] Raw material preparation: The co-catalyst is methylaluminoxane (MAO), and the main catalyst is formula (III 2 ), X=Y is Cl, M is Pd, the solvent in the solvent tank is petroleum ether, and ethylene is polymerization grade ethylene. The preparation process of the main catalyst is substantially the same as the preparation process of Example 1, which will not be repeated here.

[0123] Formula (III 2 )

[0124] Polymerization reaction: petroleum ether and methylaluminoxane are mixed, and then mixed with the main catalyst and put into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 60°C, the pressure is 1.5MPa, the ethylene flow rate is 10.0kg / h, the residence time is 1.5h, the catalyst single reactor concentration is 2mg / L, and the molar ratio of methylaluminoxane to the main catalyst is 1000 to obtain a reaction gel.

[0125] Post-processing process: The reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent. The flash temperature is controlled at 110℃, the pressure is controlled at 0.05MPa, and the glue liquid concentration is controlled at 25%. The glue liquid is transferred to a multi-stage series drying tower for three-stage stripping drying to recover the solvent. The stripping temperature is controlled at 100℃ and the pressure is controlled at 0.06MPa.

[0126] The rubber liquid dried by three-stage stripping passes through an automatic filtering device, then washed with water to cool down, the temperature is controlled at 30°C, filtered again, and enters the extrusion equipment for dehydration. After extrusion dehydration, it is dried at 85°C. The water content of the rubber particles is less than 0.15%. The rubber particles enter the screw extruder, are screw extruded and granulated, the screw speed is 50r / min, the temperature is controlled at 110°C, and then automatically packaged to prepare E-POE2.

[0127] Embodiment 3:

[0128] Preparation process of E-POE3:

[0129] Raw material preparation: the co-catalyst is sesquiethylaluminum, the main catalyst is formula (III 3 ), X is Cl, Y is Me, M is Pd, the solvent in the solvent tank is n-heptane, and ethylene is polymerization grade ethylene. The preparation process of the main catalyst is substantially the same as the preparation process of Example 1, and will not be repeated here.

[0130] Formula (III 3 )

[0131] Polymerization reaction: n-heptane and sesquiethylaluminum are mixed, and then mixed with the main catalyst and put into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 55°C, the pressure is 1.8MPa, the ethylene flow rate is 8.0 kg / h, the residence time is 1.5h, the catalyst single reactor concentration is 3mg / L, and the molar ratio of sesquiethylaluminum to the main catalyst is 1500 to obtain a reaction gel.

[0132] Post-treatment process: The reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent. The flash temperature is controlled at 120℃, the pressure is controlled at 0.05MPa, and the glue liquid concentration is controlled at 35%. The glue liquid is transferred to a multi-stage series drying tower for three-stage stripping drying to recover the solvent. The stripping temperature is controlled at 110℃ and the pressure is controlled at 0.06MPa.

[0133] The rubber liquid dried by three-stage stripping passes through an automatic filtering device, then washed with water to cool down, the temperature is controlled at 35°C, filtered again, and enters the extrusion equipment for dehydration. After extrusion dehydration, it is dried at 90°C. The water content of the rubber particles is less than 0.15%. The rubber particles enter the screw extruder, are screw extruded and granulated, the screw speed is 50r / min, the temperature is controlled at 110°C, and then automatically packaged to prepare E-POE3.

[0134] Embodiment 4:

[0135] Preparation process of E-POE4:

[0136] Raw material preparation: The co-catalyst is diethylaluminum chloride (DEAC), and the main catalyst is formula (III 4 ), X and Y are both Cl, M is Ni, the solvent in the solvent tank is n-heptane, and ethylene is polymerization grade ethylene. The preparation process of the main catalyst is substantially the same as the preparation process of Example 1, and will not be repeated here.

[0137] Formula (III 4 )

[0138] Polymerization reaction: n-heptane and DEAC are mixed, and then mixed with the main catalyst and put into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 50°C, the pressure is 2.0MPa, the ethylene flow rate is 10.0kg / h, the residence time is 1.5h, the catalyst single reactor concentration is 4mg / L, and the molar ratio of DEAC to the main catalyst is 1000 to obtain a reaction gel.

[0139] Post-processing process: The reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent. The flash temperature is controlled at 110℃, the pressure is controlled at 0.05MPa, and the glue liquid concentration is controlled at 30%. The glue liquid is transferred to a multi-stage series drying tower for three-stage stripping drying to recover the solvent. The stripping temperature is controlled at 110℃ and the pressure is controlled at 0.06MPa.

[0140] The rubber liquid dried by three-stage stripping passes through an automatic filtering device, then washed with water to cool down, the temperature is controlled at 30°C, filtered again, and enters the extrusion equipment for dehydration. After extrusion dehydration, it is dried at 100°C, and the water content of the rubber particles is less than 0.15%. The rubber particles enter the screw extruder, are screw extruded and granulated, the screw speed is 50r / min, the temperature is controlled at 110°C, and then automatically packaged to prepare E-POE4.

[0141] Embodiment 5:

[0142] Preparation process of E-POE5:

[0143] Raw material preparation: The co-catalyst is modified methyl aryl oxane (MMAO), and the main catalyst is formula (III 5 ), X=Y is Br, M is Ni, the solvent in the solvent tank is toluene, and ethylene is polymerization grade ethylene. The preparation process of the main catalyst is substantially the same as the preparation process of Example 1, and will not be repeated here.

[0144] Formula (III 5 )

[0145] Polymerization reaction: n-heptane is mixed with MMAO, and then mixed with the main catalyst into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 50°C, the pressure is 1.5MPa, the ethylene flow rate is 10.0kg / h, the residence time is 2.0h, the catalyst single reactor concentration is 3mg / L, and the molar ratio of MMAO to the main catalyst is 500.

[0146] Post-processing process: The reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent. The flash temperature is controlled at 110℃, the pressure is controlled at 0.05MPa, and the glue liquid concentration is controlled at 30%. The glue liquid is transferred to a multi-stage series drying tower for three-stage stripping drying to recover the solvent. The stripping temperature is controlled at 110℃ and the pressure is controlled at 0.06MPa.

[0147] The rubber liquid dried by three-stage stripping passes through an automatic filtering device, then washed with water to cool down, the temperature is controlled at 35°C, filtered again, and enters the extrusion equipment for dehydration. After extrusion dehydration, it is dried at 90°C. The water content of the rubber particles is less than 0.15%. The rubber particles enter the screw extruder, are screw extruded and granulated, the screw speed is 50r / min, the temperature is controlled at 110°C, and then automatically packaged to prepare E-POE5.

[0148] Embodiment 6:

[0149] This Example 6 is substantially the same as Example 1, except that the co-catalyst used is DEAC to prepare E-POE6.

[0150] Embodiment 7:

[0151] This Example 7 is substantially the same as Example 2, except that the molar ratio of MAO to the main catalyst is 1500, and E-POE7 is prepared.

[0152] Embodiment 8:

[0153] This Example 8 is generally the same as Example 3, except that the catalyst concentration in a single kettle is 10 μg / L, and E-POE8 is prepared.

[0154] Embodiment 9:

[0155] This Example 9 is substantially the same as Example 4, except that the co-catalyst is sesquiethylaluminum to prepare E-POE9.

[0156] Embodiment 10:

[0157] This Example 10 is substantially the same as Example 5, except that the molar ratio of DEAC to catalyst is 1500 times, and E-POE10 is prepared.

[0158] Comparative Example 1:

[0159] The preparation process of this comparative example 1 is substantially the same as that of Example 1, except that the post-treatment process adopts a dry deashing process. The dry deashing post-treatment process is as follows: the reaction glue liquid enters the flash tank for flash evaporation to recover ethylene and solvent, the flash temperature is controlled at 110°C, the pressure is controlled at 0.05MPa, and the glue concentration is controlled at 30%. The polymer glue liquid after flash evaporation is transferred to the refining deashing unit through a metering pump, and the glue liquid is deashed to maintain the refining tower pressure difference below 7 MPa. The glue liquid is transferred to the devolatilization granulation unit, and the process dry deashing process used is preferably after vacuum deashing in the first, second and multi-stage steps. The first deashing temperature is controlled at 110°C and the rotation speed is 80r / min; the second deashing temperature is controlled at 130°C and the rotation speed is 70r / min; the third deashing temperature is controlled at 170°C and the rotation speed is 30r / min to prepare E-POE1'.

[0160] Comparative Example 2:

[0161] Preparation process of polyethylene particles:

[0162] Raw material preparation: the co-catalyst is diethylaluminum monochloride, the main catalyst is a catalyst with a structure shown in formula (V), X=Y is Br, M is Ni, the solvent in the solvent tank is cyclohexane, and the ethylene is polymerization grade ethylene.

[0163] Formula (V)

[0164] Polymerization reaction: Cyclohexane and diethylaluminum chloride are mixed, and then mixed with the main catalyst and put into the reactor to react with ethylene. The reaction process uses three reactors in series to react continuously, and the polymerization temperature is controlled at 40°C, the pressure is 2.5MPa, the ethylene flow rate is 12.5kg / h, the residence time is 1.5h, the catalyst single reactor concentration is 3mg / L, and the molar ratio of diethylaluminum chloride to the main catalyst is 750 to obtain polyethylene slurry.

[0165] Post-processing process: The polyethylene slurry is filtered and dried to obtain polyethylene particles.

[0166] The performance tests were performed on the products prepared in Examples 1 to 10 of the present invention and Comparative Examples 1 and 2, and the indicators obtained from the tests are shown in Table 2 below.

[0167] Table 2 Product indicators obtained from the test of the embodiments and comparative examples

[0168]

[0169] By comparing Examples 1 to 10, it can be seen that the polyolefin elastomers prepared by the main catalysts of different structures have lower ash and volatile content, higher purity, and better application prospects. Comparative Example 2 produces polyethylene, which has better cleanliness, but poor branching and elasticity, making it difficult to use as an elastomer. In addition, the products prepared by Comparative Example 1 and Comparative Example 2 have higher ash and volatile content, higher impurity content, and are difficult to further apply.

[0170] The E-POE products prepared based on the above Examples 1 to 5 were applied to photovoltaic encapsulation films, and their related properties were tested. The raw material formula used is shown in Table 3 below.

[0171] Table 3 Photovoltaic encapsulation film usage formula

[0172]

[0173] Application Example 1:

[0174] 100 parts of E-POE1 in Example 1, 6 parts of PE grafted maleic anhydride resin, 0.1 parts of silane coupling agent ethylene triethoxysilane, 0.1 parts of cross-linking agent diisopropyl peroxide, 0.15 parts of anti-aging agent 2,6-di-tert-butyl-4-methylphenol, and 0.1 parts of anti-ultraviolet 2-(2-hydroxy-5-methylphenyl)benzotriazole were mixed evenly, and granulated in a twin-screw extruder to prepare reinforced resin modified E-POE granules. The processing temperature was 130°C, the extrusion film forming temperature was 110°C, and the film thickness was 0.3 mm to prepare an E-POE film.

[0175] Application Example 2:

[0176] The preparation process is substantially the same as that of Application Example 1, except that the E-POE2 in Example 2 is used to prepare the E-POE film.

[0177] Application Example 3:

[0178] The preparation process is substantially the same as that of Application Example 1, except that the E-POE3 in Example 3 is used to prepare the E-POE film.

[0179] Application example 4:

[0180] The preparation process is substantially the same as that of Application Example 1, except that the E-POE4 in Example 4 is used to prepare the E-POE film.

[0181] Application Example 5:

[0182] The preparation process is substantially the same as that of Application Example 1, except that E-POE5 in Example 5 is used to prepare the E-POE film.

[0183] Comparative application example 1:

[0184] The preparation process is substantially the same as that of Application Example 1, except that Dow Chemical POE8200 polyolefin elastomer resin is used to prepare the POE film.

[0185] The properties of the adhesive films prepared in Examples 1 to 5 and Comparative Application Example 1 were tested, and the test results are shown in Table 4 below.

[0186] Table 4 Film performance parameters of application examples and comparative application examples

[0187]

[0188] As can be seen from the parameter comparison in Table 4, the E-POE film prepared by the present invention has generally better tensile strength, adhesion, and transmittance than the POE film, and its aging effect is comparable to that of POE. Therefore, the comprehensive performance of the E-POE of the present invention is excellent, and basically meets the requirements of the photovoltaic module for the film. The preparation process and application process of the present invention are simple, the preparation process is convenient, and it is convenient for large-scale production and application promotion.

[0189] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A ligand compound, characterized in that The ligand compound has a structure as shown in formula (I) or formula (II): Formula (I), Formula (II); wherein b1, b2, b3, R1, and R2 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy, C6-C 30 Aryl, C 10 ~C 50 Any of the fused ring aromatic groups; R1 and R2 are connected to form a ring or not. In the case where R1 and R2 are connected to form a ring, R1 and R2 are connected to form a C 10 ~C 50 Fused ring aromatic groups; b4 and b5 are independently selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl, C2~C6 alkenyl, C2~C6 alkynyl, and C1~C5 alkoxy; c1, c2, c3 are independently selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl, C2~C6 alkenyl, C2~C6 alkynyl, C1~C5 alkoxy, and phenoxy; R3 and R4 are independently selected from hydrogen, substituted or unsubstituted C1~C5 alkyl, C3~C 10 Any one of a cycloalkyl group and a substituted phenyl group, wherein the substituent of the substituted phenyl group comprises a C1 to C5 alkyl group; In the case where there is a substituent on the substituted or unsubstituted group, the substituent is selected from halogen, C1~C5 alkyl, C6~C 12 Aryl, C3-C 30 Any of the heteroaryl groups.

2. The ligand compound according to claim 1, characterized in that b1, b2, and b3 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, and when there is a substituent on the C1-C5 alkyl, the substituent is selected from C6-C 12 Aryl; R1 and R2 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl and tert-butyl; When R1 and R2 are connected to form a ring, R1 and R2 are connected to form any one of naphthyl, fluorenyl, acenaphthenyl and phenanthryl; b4 and b5 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl and methoxy; c1, c2, c3 are independently selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl, and phenoxy. When there is a substituent on the C1~C5 alkyl, there are 1 to 3 substituents, and each substituent is independently selected from C6~C 12 Any of aryl, thiophene, furan, and selenophene; R3 and R4 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexane, and substituted phenyl.

3. The ligand compound according to claim 1, characterized in that The ligand compound has a structure shown in any one of formula (I1) to formula (I6) and formula (II1) to formula (II3): Formula (I1), Formula (I2), Formula (I3), Formula (I4), Formula (I5), Formula (I6), Formula (II1), Formula (II2), Formula (II3).

4. A method for preparing the ligand compound according to any one of claims 1 to 3, characterized in that: The preparation method comprises: The compound represented by formula (A) , the compound represented by formula (B) , the compound represented by formula (C) Carry out a condensation reaction to obtain a ligand compound represented by formula (I); or The compound represented by formula (D) , the compound represented by formula (E) A condensation reaction is carried out to obtain a ligand compound represented by formula (II).

5. The preparation method according to claim 4, characterized in that: The catalyst used in the condensation reaction includes p-toluenesulfonic acid, the temperature of the condensation reaction is 110-130° C., and the reaction time is 11-13 hours.

6. A complex, characterized in that The complex has a structure as shown in formula (III) or formula (IV): Formula (III), Formula (IV); wherein b1, b2, b3, R1, and R2 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy, C6-C 30 Aryl, C 10 ~C 50 Any of the fused ring aromatic groups; R1 and R2 are connected to form a ring or not. In the case where R1 and R2 are connected to form a ring, R1 and R2 are connected to form a C 10 ~C 50 Fused ring aromatic groups; b4 and b5 are independently selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl, C2~C6 alkenyl, C2~C6 alkynyl, and C1~C5 alkoxy; c1, c2, c3 are independently selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl, C2~C6 alkenyl, C2~C6 alkynyl, C1~C5 alkoxy, and phenoxy; R3 and R4 are independently selected from hydrogen, substituted or unsubstituted C1~C5 alkyl, C3~C 10 Any one of a cycloalkyl group and a substituted phenyl group, wherein the substituent of the substituted phenyl group comprises a C1 to C5 alkyl group; In the case where there is a substituent on the substituted or unsubstituted group, the substituent is selected from halogen, C1~C5 alkyl, C6~C 12 Aryl, C3-C 30 Any of the heteroaryl groups; M is selected from any one of Ni, Pd, Fe, and Co; X and Y are each independently selected from any one of halogen, methyl, phenyl and acetylacetonato.

7. A method for preparing the complex according to claim 6, characterized in that: The method comprises: A ligand compound having a structure as shown in formula (I) or formula (II) is subjected to a coordination reaction with a divalent metal compound to obtain a complex having a structure as shown in formula (III) or formula (IV); Wherein, the divalent metal compound includes at least one of ethylene glycol dimethyl ether nickel bromide, nickel chloride, nickel iodide, allyl nickel chloride, triphenylphosphine nickel chloride, palladium chloride, and alkyl palladium chloride.

8. Use of the complex as claimed in claim 6 as a late transition metal catalyst in a solution polymerization process of a polyolefin elastomer.

9. The use according to claim 8, characterized in that: The solution polymerization process of the polyolefin elastomer uses ethylene as the only olefin monomer raw material.

10. The use according to claim 9, characterized in that: The solution polymerization process of the polyolefin elastomer comprises: Adding a co-catalyst, the complex and ethylene monomer into an organic solvent to allow the ethylene monomer to undergo a homopolymerization reaction; The cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, sesquiethylaluminum, methylaluminoxane, modified methylaluminoxane, triphenylcarbon tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

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