Ligand Compound and Preparation Method Thereof, Complex and Preparation Method Thereof, Application

Abstract

The present invention provides a ligand compound and a preparation method thereof, a complex and a preparation method thereof, and an application, belonging to the technical field of polyolefins. The ligand compound has a structure shown in formula (I) or formula (II), formula (I), formula (II); b1, b2, b3, R1, and R2 are each 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 one of fused-ring aryls; R1 and R2 are connected to form a ring or not; b4 and b5 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy; c1, c2, and c3 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy, phenoxy; R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C3-C 10 cycloalkyl, 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 thereof, and an application. Background Art

[0002] Polyolefin elastomer (POE) is a kind of polyolefin elastomer material copolymerized from ethylene and α-olefins (such as 1-octene, 1-butene, etc.). This catalytic system mainly uses a constrained geometry metallocene catalyst (CGC catalyst) for catalysis. Since the content of comonomers in the POE molecular chain is high and the density is low, 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 processability of thermoplastic resin.

[0003] Polyolefin elastomers are usually prepared by copolymerizing expensive long-chain α-olefins with ethylene as comonomers. These α-olefins mainly come from imports, and the prices of the CGC catalysts and α-olefins used are relatively high, 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 a ligand compound and a preparation method thereof, a complex and a preparation method thereof, and an application.

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

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

[0007] b1, b2, b3, R1, and R2 are each independently selected from any one of 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 one of fused-ring aryls; R1 and R2 are either connected to form a ring or not connected to form a ring. When R1 and R2 are connected to form a ring, R1 and R2 are connected to form a C 10 ~C 50 fused-ring aryl; b4 and b5 are each 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 each 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 each independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl, C3-C10 Any one of cycloalkyl and substituted phenyl, wherein the substituent of the substituted phenyl includes C1-C5 alkyl; when 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 one of heteroaryl.

[0008] According to an embodiment of the present invention, b1, b2, and b3 are each independently selected from hydrogen and substituted or unsubstituted C1-C5 alkyl. When there is a substituent on the C1-C5 alkyl, the substituent is selected from C6-C 12 aryl; R1 and R2 are each independently selected from any one of hydrogen, methyl, ethyl, isopropyl, and tert-butyl; R1 and R2 are connected in a ring or not connected in a ring. When R1 and R2 are connected in a ring, R1 and R2 are connected to form any one of naphthyl, fluorenyl, acenaphthylenyl, and phenanthryl; b4 and b5 are each independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, and methoxy; c1, c2, and c3 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, and phenoxy. When there is a substituent on the C1-C5 alkyl, there are 1-3 substituents, and each substituent is independently selected from C6-C 12 aryl, thiophene, furan, and selenophene; R3 and R4 are each 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 a structure shown in any one of formulas (I1)-(I6) and (II1)-(II3):

[0010] Formula (I1), Formula (I2),

[0011] Formula (I3), Formula (I4),

[0012] Formula (I5), Formula (I6),

[0013] Formula (II1), Formula (II2),

[0014] Formula (II3).

[0015] According to an embodiment of another aspect of the present invention, a preparation method of the ligand compound as described above is provided. The preparation method includes: reacting a compound represented by formula (A) and the compound shown in formula (B) and the compound shown in formula (C) are subjected to a condensation reaction to obtain the ligand compound shown in formula (I); or the compound shown in formula (D) and the compound shown in formula (E) are subjected to a condensation reaction to obtain the ligand compound shown in formula (II).

[0016] According to the embodiments 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 h.

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

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

[0019] wherein, b1, b2, b3, R1, and R2 are each 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 one of fused-ring aryl; R1 and R2 are connected to form a ring or not connected to form a ring. 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 aryl; b4 and b5 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy; c1, c2, and c3 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy, phenoxy; R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C3-C 10 cycloalkyl, substituted phenyl, and the substituents of the substituted phenyl include C1-C5 alkyl; in the case where there are substituents on the substituted or unsubstituted group, the substituents are selected from halogen, C1-C5 alkyl, C6-C 12 aryl, C3-C 30 any one of heteroaryl; M is selected from any one of Ni, Pd, Fe, and Co; X and Y are each independently selected from halogen, methyl, phenyl, and acetylacetonyl.

[0020] According to an embodiment of another aspect of the present invention, there is provided a method for preparing a complex as described above, the method comprising: performing a coordination reaction between a ligand compound having a structure represented by formula (I) or formula (II) and a divalent metal compound to obtain a complex having a structure represented by formula (III) or formula (IV); the divalent metal compound includes at least one of nickel bromide dimethoxyethane, nickel chloride, nickel iodide, nickel allyl chloride, nickel chloride triphenylphosphine, palladium chloride, and alkyl palladium chloride.

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

[0022] According to an embodiment of the present invention, ethylene is used as the sole olefin monomer raw material in the solution polymerization process of polyolefin elastomers.

[0023] According to an embodiment of the present invention, the solution polymerization process of polyolefin elastomers includes: adding a cocatalyst, a complex, and an ethylene monomer to an organic solvent to cause the ethylene monomer to undergo a homopolymerization reaction; the cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, sesquialuminum ethyl, methylaluminoxane, modified methylaluminoxane, triphenylcarbenium 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 pyridineimine as the backbone, and at one end of the diimine backbone or pyridineimine backbone, that is, the ortho-substituent of the N-aryl, a structure with a large steric hindrance is used, which has a strong π-conjugation effect. At the other end of the diimine backbone or pyridineimine backbone, a group with a small steric hindrance is connected, so that when the ligand compound coordinates with the divalent metal to form a bond, it has high thermal stability. By setting such an asymmetric structure, it helps to improve the effective coordination of olefin monomers and promote a certain degree of chain walking of olefin monomers, thereby helping to prepare polyolefin elastomers with a suitable degree of branching. Detailed Embodiments

[0025] The terms used herein are merely for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the presence of features, steps, operations, but does not exclude the presence 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.", generally, it should be interpreted according to the meaning that those skilled in the art usually understand this expression (for example, "a system having at least one of A, B, and C" should include, but not be limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", generally, it should be interpreted according to the meaning that those skilled in the art usually understand this expression (for example, "a system having at least one of A, B, or C" should include, but not be limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.).

[0027] In the present invention, the group of "substituted or unsubstituted" may be substituted with one substituent or multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the present invention involves the same expression, it has the same meaning, and the selection range of the substituents is as shown above and will not be elaborated one by one.

[0028] In the present invention, "independently of each other" means that when its subject has multiple, they may be the same or different from each other.

[0029] In the present invention, for the expression of chemical elements, unless otherwise specified, it usually includes the concept of isotopes with the same chemical properties. For example, the expression of "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., and will not be elaborated further.

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

[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. For example, as an example of C1~C 20 Examples of alkyl may include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

[0032] The polyolefin elastomer (POE) commonly used in the related art is mostly formed by copolymerization of ethylene and α-olefins. POE has the following advantages: a relatively narrow molecular weight distribution, a relatively high α-olefin content, a relatively low density and crystallinity, and exhibits excellent mechanical properties, such as a high elongation at break, high elasticity, excellent impact resistance and low-temperature resistance. It contains a non-polar saturated single-bond chain structure and does not require vulcanization, making POE have heat resistance, heat-oxygen aging resistance, ultraviolet resistance, water vapor resistance and corrosion resistance. It has both the plasticity of a crystalline resin phase and the high elasticity of an amorphous rubber phase, can undergo plastic flow, has excellent processing rheological properties, is easy to extrude or injection mold and other processing and forming, and is not prone to flexural deformation. It has excellent high transparency, toughness and compatibility, and can be widely used for toughening and modification of olefin polymers.

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

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

[0035] In the related art, when using a common complex of an asymmetric α-diimine as a catalyst, in the case of catalyzing ethylene homopolymerization, it usually catalyzes the formation of polyethylene, that is, mainly presents a crystalline resin phase. However, the complex of the present invention adjusts the chain walking of ethylene monomers during the catalysis of ethylene homopolymerization, 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, a ligand compound having a structure shown in formula (I) or formula (II) is provided:

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

[0038] wherein, b1, b2, b3, R1, and R2 are each independently selected from hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C5 alkoxy group, a C6-C 30 aryl group, C 10 ~C 50Any one of polycyclic aryl groups; R1 and R2 are either connected to form a ring or not. When R1 and R2 are connected to form a ring, R1 and R2 are connected to form C 10 ~C 50 a polycyclic aryl group; b4 and b5 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, and C1-C5 alkoxy groups; c1, c2, and c3 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, C1-C5 alkoxy groups, and phenoxy groups; R3 and R4 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl groups, C3-C 10 any one of cycloalkyl groups and substituted phenyl groups, and the substituents of the substituted phenyl groups include C1-C5 alkyl groups; when there are substituents on the substituted or unsubstituted groups, the substituents are selected from any one of halogen, C1-C5 alkyl groups, C6-C 12 aryl groups, C3-C 30 any one of heteroaryl groups.

[0039] For the ligand compound shown in formula (I), using α-diamine as the main skeleton, a bulky aryl group with a substituent such as diphenylmethyl is used as the ortho-substituent of the N-aryl at one end of the diamine skeleton. It has a strong conjugation effect, can enhance the electron-donating ability of the ligand compound, and helps to regulate the electron cloud density of the metal center of the subsequent prepared complex. When catalyzing the polymerization of ethylene subsequently, it helps to improve the selectivity and activity of the polymerization reaction and enhance the thermal stability of the prepared polyolefin elastomer.

[0040] A group with a smaller steric hindrance is used as the ortho-substituent of the N-aryl at the other end of the diamine skeleton, forming an asymmetric structure. Such an asymmetric structure promotes the effective coordination of olefin monomers and promotes the chain walking of olefin monomers within a certain range during the reaction, which helps to prepare a polyolefin elastomer with the required degree of branching, making the polyolefin elastomer have both the high elasticity of rubber and the plasticity of thermoplastic resin.

[0041] For the ligand compound shown in formula (II), with a mechanism similar to that of the diamine skeleton, an asymmetric structure is constructed on both sides of the main skeleton of pyridine imine, which promotes the chain walking of olefin monomers within a certain range during the polymerization reaction. Similarly, it helps to prepare a polyolefin elastomer with a moderate degree of branching, making the polyolefin elastomer have both the high elasticity of rubber and the plasticity of thermoplastic resin.

[0042] Since the present invention uses the ligand compound shown in formula (I) or formula (II), it avoids the use of expensive α-olefins and metallocene catalysts, can significantly reduce the production cost, and at the same time can improve the thermal stability of the prepared polyolefin elastomer, which is beneficial for industrial applications.

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

[0044] Preferably, b1, b2, and b3 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl groups. When there are substituents on the C1-C5 alkyl groups, the substituents are selected from C6-C 12 aryl groups; more preferably, b1 and b2 are each independently selected from hydrogen, methyl, ethyl, isopropyl, and tert-butyl, where methyl, ethyl, isopropyl, and tert-butyl are substituted or unsubstituted. When b1, b2, and b3 are substituted, the substituents are selected from at least one of phenyl, biphenyl, terphenyl, benzhydryl, naphthyl, fluorene, and spirofluorene. b1 and b2 can be the same or different. b3 is selected from hydrogen, methyl, ethyl, isopropyl, and tert-butyl. b3 can be the same as at least one of b1 and b2, or can be different from both b1 and b2.

[0045] Preferably, R1 and R2 are each 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, acenaphthylenyl, and phenanthrenyl, more preferably acenaphthylenyl; b4 and b5 are each independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, and methoxy.

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

[0047] Preferably, c1, c2, and c3 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C5 alkyl groups, and phenoxy groups. When there are substituents on the C1-C5 alkyl group, there are 1-3 substituents, and each substituent is independently selected from any one of C6-C 12 aryl groups, thiophene, furan, and selenophene; more preferably, c1 and c3 are each independently selected from substituted C1-C5 alkyl groups and phenoxy groups. There are 2 substituents on the C1-C5 alkyl group, and each substituent is independently selected from any one of benzyl, thiophene, and furan. c1 and c3 can be the same or different. c2 is selected from hydrogen, methyl, ethyl, isopropyl, and tert-butyl. c2 can be the same as at least one of c1 and c3, or different from both c1 and c3.

[0048] Even more preferably, c1 and c3 are each independently methyl substituted with 2 benzyl groups, methyl substituted with 2 phenyl groups, methyl substituted with 2 thiophene groups, or phenoxy; c2 is methyl.

[0049] Preferably, R3 and R4 are each independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, and substituted phenyl groups; more preferably, R3 is methyl, and R4 is tert-butyl, cyclohexane, or 1,3-diisopropyl-5-methylbenzene.

[0050] Using pyridine imine as the main backbone, similar to the mechanism of α-diimine, a cyclic structure with a large steric hindrance is constructed at the ortho position of the N-aryl on the side of the pyridine imine far from the pyridine group. It has a large conjugation effect, which helps to improve the selectivity and activity of the polymerization reaction and enhance the thermal stability of the prepared polyolefin elastomer. The substituents connected on the side close to the pyridine group have a small steric hindrance. When forming a complex to catalyze the homopolymerization of ethylene, it promotes the insertion of olefin monomers into the metal center and performs a certain range of chain walking, which helps to prepare a polyolefin elastomer with the required degree of branching.

[0051] According to the examples of the present invention, the ligand compound has a structure shown in any one of Formula (I1)-(I6) and Formula (II1)-(II3):

[0052] Formula (I1), Formula (I2),

[0053] Formula (I3), Formula (I4),

[0054] Formula (I5), Formula (I6),

[0055] Formula (II1), Formula (II2),

[0056] Formula (II3).

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

[0058] According to an embodiment of another aspect of the present invention, a preparation method of the ligand compound as described above is provided, including: reacting the compound shown in formula (A) , the compound shown in formula (B) , the compound shown in formula (C) by condensation reaction to obtain the ligand compound shown in formula (I). Or reacting the compound shown in formula (D) , the compound shown in formula (E) by condensation reaction to obtain the ligand compound shown in formula (II).

[0059] According to the embodiment of the present invention, by subjecting several monomers to a condensation reaction, a diimine ligand compound or a pyridineimine ligand compound with an asymmetric structure is prepared, which helps to promote the chain walking of ethylene during the subsequent formation of a complex to catalyze the homopolymerization of ethylene, thereby preparing a polyolefin elastomer.

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

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

[0062] Preferably, the molar ratio of the three compounds added is 1:1:1, for example, they can all 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 shown in formula (II) is as follows: Mix the compound shown in formula (D) and the compound shown in formula (E) in a 100 mL round-bottom flask, add p-toluenesulfonic acid and the first solvent, and then place it in an oil bath at 120 °C for a condensation reaction (water separation reaction). After the reaction is completed, the first solvent is concentrated under vacuum, and the obtained crude product is separated by column chromatography. The separation column uses a neutral alumina column (eluent V(ethyl acetate) / V(polyethylene) = 1 / 50) to obtain the pyridine imine ligand compound (shown in formula (II)).

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

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

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

[0067] Wherein, b1, b2, b3, R1, and R2 are each 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 one of fused polycyclic aryl; R1 and R2 are connected to form a ring or not connected to form a ring. In the case where R1 and R2 are connected to form a ring, R1 and R2 are connected to form C 10 ~C 50 fused polycyclic aryl; b4 and b5 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy; c1, c2, and c3 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C5 alkoxy, phenoxy; R3 and R4 are each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, C3-C 10 cycloalkyl, substituted phenyl, and the substituents of the substituted phenyl include C1-C5 alkyl; in the case where there are substituents on the substituted or unsubstituted group, the substituents are selected from halogen, C1-C5 alkyl, C6-C12 Any one of aryl, C3-C 30 Any one of heteroaryl.

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

[0069] It should be noted that the preferred group ranges of b1, b2, b3, R1, R2, R3, R4, c1, c2, c3 of the above complex are the same as those of the ligand compound, and will not be elaborated 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 regulatory effect on the catalytic polymerization of olefin monomers. By constructing an appropriate steric space, the spatial position of metal insertion can be made relatively restricted, thereby restricting the chain walking reaction of metal groups within a certain space range, further improving the selectivity and yield of the reaction, preventing the occurrence of unnecessary side reactions, improving the controllability of the reaction, and being conducive to preparing polyolefin elastomers with a certain degree of branching.

[0071] According to the embodiments of the present invention, the complex has a structure shown in any one of Formula (III1) to Formula (III6), Formula (IV1) to Formula (IV3):

[0072] Formula (III1), Formula (III2),

[0073] Formula (III3), Formula (III4),

[0074] Formula (III5), Formula (III6),

[0075] Formula (IV1), Formula (IV2),

[0076] Formula (IV3).

[0077] According to the embodiments of the present invention, the preparation process of the above complex is relatively simple, and when catalyzing the homopolymerization of ethylene, 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 an embodiment of another aspect of the present invention, there is provided a method for preparing a complex as described above, comprising: subjecting a ligand compound having a structure represented by formula (I) or formula (II) to a coordination reaction with a divalent metal compound to obtain a complex having a structure represented by formula (III) or formula (IV); wherein, the divalent metal compound includes at least one of nickel bromide dimethoxyethane, nickel chloride, nickel iodide, nickel allyl chloride, nickel chloride triphenylphosphine, palladium chloride, and alkyl palladium chloride, and wherein the alkyl palladium chloride may be methyl palladium chloride, ethyl palladium chloride, etc.

[0079] In one specific embodiment, the ligand compound having a structure represented by formula (I) or formula (II) is mixed with the divalent metal compound in a 100 mL Schlenk flask in a glove box, a second solvent is added and then a coordination reaction is carried out. After the reaction is completed, vacuum concentration is carried out, and then recrystallization is carried out using anhydrous n-hexane. After suction filtration, washing is carried out using n-hexane to obtain a complex having a structure represented by formula (III) or formula (IV).

[0080] Preferably, the conditions of 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 h.

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

[0082] Using the above complex can generate a metal center with high activity, and this metal center can effectively activate olefin monomers (such as ethylene, α-olefins, etc.), promote the insertion of olefin monomers into the metal-carbon bond for chain growth, thereby realizing the polymerization reaction. The asymmetric diimine ligand backbone or pyridineimine backbone 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 degree of branching, so that the prepared polyolefin elastomer has both elasticity and plasticity.

[0083] The α-olefins may include, for example, one or more of propylene, 1-butene, 1-hexene, 1-octene, methyl methacrylate, isobutyl methacrylate, etc.

[0084] According to an embodiment of the present invention, the solution polymerization process of polyolefin elastomer uses ethylene as the only olefin monomer raw material. The complex provided by the present invention can use ethylene as the only olefin monomer raw material, without using α-olefin as a comonomer, and produce vinyl polyolefin elastomer through solution polymerization. This complex has a high abundance, avoids the application 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 requirements in fields such as photovoltaic, automotive, toughening and strengthening, etc.

[0085] According to an embodiment of the present invention, the solution polymerization process of polyolefin elastomer includes: adding a cocatalyst, a complex, and an ethylene monomer into an organic solvent to enable the ethylene monomer to carry out homopolymerization reaction; the cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, sesquialuminum ethyl, methylaluminoxane, modified methylaluminoxane, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. Among them, the cocatalyst is used in combination with the corresponding complex as needed. Since this is not the focus of the present invention, it will not be elaborated one by one here.

[0086] The organic solvent is at least one of C5-C 30 alkanes or isoparaffins, alkyl-substituted cyclohexanes, benzene or homologues of benzene, dichloromethane, or a mixture of halogenated alkanes and alkanes (containing halogenated alkanes or benzene). Cyclopentane, toluene, heptane, and their mixtures are preferred, and heptane and cyclohexane are more preferred.

[0087] The specific structure of the complex of the present invention enables 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 and material consumption are significantly reduced. In the complex with an asymmetric α-diimine skeleton and / or pyridine-imine skeleton, there is a large steric hindrance at the ortho position of aniline on one side, which makes the complex have higher thermal stability. When the para-position electron-donating group (such as methyl or methoxy) can further increase the thermal stability of the complex, the combined effect further improves the stability of catalyzing ethylene homopolymerization. The small steric hindrance at the ortho position on the other side of the complex mainly acts on the effective coordination of ethylene monomers, promoting a certain degree of chain walking of ethylene monomers, and thus vinyl polyolefin elastomer can be prepared.

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

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

[0090] The solution polymerization process of the present invention further includes: subjecting the obtained polyolefin rubber solution to wet deashing and devolatilization in sequence. Specifically, the rubber solution obtained after passing through the three polymerization reactors is transported to a flash tank for ethylene monomer and solvent recovery, and then through condensation, compression, and purification, controlling the rubber solution concentration at 20 - 60%, and then transferring the rubber solution to a stripping and washing kettle. After 3 - stage stripping and washing, the solvent in the rubber particles is recovered, and then filtration, dehydration, and drying are carried out in sequence, and then packaging to obtain the finished product of vinyl polyolefin elastomer. The process of the present invention is beneficial to preparing high - performance vinyl polyolefin elastomers with low cost, low material consumption, low ash content, and low volatile content. The vinyl polyolefin elastomer has broad application prospects in the fields of photovoltaics, automobiles, material toughening and strengthening, etc.

[0091] In one specific 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 a refining unit to remove impurities. The externally purchased ethylene or other α - olefins are refined to remove impurities to prepare polymerization - grade monomers. The main catalyst (i.e., the complex) and the cocatalyst are respectively processed to reduce the concentration for polymerization use.

[0094] Polymerization reaction:

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

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

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

[0098] Post-treatment process:

[0099] The glue solution from the third reactor is transported into a flash tank for the recovery of olefin monomers and solvents. The recovered solvents are transferred into a solvent recovery tank. After the recovered olefin monomers are subjected to condensation, compression, and purification, they are transferred into ethylene recovery for standby. The glue solution concentration is controlled at 20% - 60%.

[0100] Transfer the glue solution to a stripping and washing kettle. After 3 - stage stripping and washing, the temperature is controlled at 90 - 150 °C and the pressure is controlled at 0 - 2 MPa. The main purpose is to recover the solvents inside the rubber particles. The washed rubber particles are transferred into a filtration unit after cooling with water washing, and then extruded to remove water. After dehydration, the rubber particles are dried and then automatically packed.

[0101] The process of 3 - stage stripping and washing is as follows: The glue solution after flash evaporation passes through a rubber particle pump into the first stripping and washing kettle. The flash evaporation temperature is 100 - 120 °C, and low - pressure steam is used for flash evaporation. After the glue solution undergoes flash evaporation and rubber washing in the kettle once, it becomes small rubber particles, removing a part of the solvents and ash. The glue solution in the first stripping and washing kettle is transferred to the second stripping and washing kettle through a rubber particle pump. The flash evaporation temperature is 100 - 120 °C, and the rubber particles are stripped and washed again to further recover the solvents and reduce the ash content in the rubber particles. The glue solution in the second stripping and washing kettle is transferred to the third stripping and washing kettle through a rubber particle pump. The flash evaporation temperature is 100 - 120 °C, and the rubber particles are stripped and washed for the third time to further recover the solvents and reduce the ash content in the rubber particles. By operating in series continuously in sequence, after multi - stage series stripping, the organic components and ash in the glue solution are significantly reduced.

[0102] In the polymerization reaction, for the feeding methods of cocatalyst, solvent, catalyst, and ethylene, the cocatalyst and solvent oil molecules are mixed in a certain proportion through a static mixer. The mixed solution and a certain amount of prepared catalyst solution pass through the static mixer again and enter the loop reactor to react with the ethylene in the reactor to prepare polyolefin elastomer.

[0103] The 3 - stage stripping and washing is a three - kettle series operation. The main purpose of each stripping and washing kettle is to reduce the volatile components in the rubber particles, recover the solvents, and reduce the production cost. The filtration unit can use a crawler - type filtration device. After the solvent oil is recovered through stripping and washing in the stripping and washing kettle, the rubber particles without oil pass through the filtration unit and enter the circulating water cooling system for temperature reduction treatment. The temperature is controlled at 30 - 50 °C, and the rubber particles are dewatered again through the filtration unit. The extrusion for water removal can be, for example, that the dewatered rubber particles enter an extruder for further extrusion to remove water. After dehydration, the rubber particles are dried under hot air and then enter the automatic packaging system for packaging. The polyolefin elastomer particles can achieve an ultra - low residual volatile content, which can reach ≤20 ppm under optimal conditions.

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

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

[0106]

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

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

[0109] The following further illustrates the present invention through examples. In the following detailed description, for the sake of explanation, many specific details are elaborated to provide a comprehensive explanation of the embodiments of the present invention. However, obviously, one or more embodiments can also be implemented without these specific details. Moreover, without conflict, the details in the following embodiments can be arbitrarily combined into other feasible embodiments.

[0110] It should be noted that the following examples illustrate the specific content of the present invention. The data given include the synthesis of ligands, the synthesis of metal compounds, and the methods of ethylene polymerization or copolymerization. Among them, the synthesis of complexes and the polymerization process are carried out under anhydrous and anaerobic conditions. All sensitive substances are stored in a glove box. All solvents are strictly dried to remove water. Ethylene gas is purified through a water-removing and oxygen-removing column. Without special instructions, all raw materials are used directly after purchase. The methods used in the following examples, such as column chromatography, etc., are all well-known methods in the art and can be carried out according to the descriptions in textbooks or relevant literature, and will not be elaborated further.

[0111] The degree of branching in the examples of the present invention is tested by high-temperature nuclear magnetic resonance. The reagent is deuterated tetrachloroethane, and the value represents the number of branched chains in 1000 carbons; the volatile content is tested according to GB / T24131.2 - 2017, the ash content 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 at a temperature of 190 °C and a load of 2.16 kg; the weight-average molecular weight M wThe molecular weight and molecular weight distribution PDI were tested in accordance with SN / T 4183-2015; the density was tested in accordance with GB / T 1033.1-2008, the volume resistivity was tested in accordance with GB / T 31838.2-2019, and the light transmittance was tested in accordance with GB / T 2410-2008.

[0112] Example 1:

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

[0114] Raw material preparation: The cocatalyst is diethylaluminum chloride, the main catalyst is the catalyst with the structure shown in formula (III1), X=Y is Br, M is Ni, the solvent in the solvent tank is cyclohexane, and the ethylene is polymerization-grade ethylene.

[0115] Formula (III1)

[0116] The preparation process of the main catalyst is as follows: Weigh the ligand shown in formula (I1) (1 mmol) and nickel bromide dimethoxyethane (1 mmol) in a 100 mL Schlenk flask in a glove box, add 30 mL of anhydrous dichloromethane, and react at room temperature for 6 h. After the reaction is completed, concentrate under vacuum, add anhydrous n-hexane for recrystallization, wash with n-hexane after filtration, and obtain the catalyst with the structure shown in formula (III1).

[0117] Polymerization reaction: Mix cyclohexane and diethylaluminum chloride, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses a three-kettle series operation for continuous reaction, controlling the polymerization temperature at 50 °C, the pressure at 2.5 MPa, the ethylene flow rate at 12.5 kg / h, the residence time at 1.5 h, the single-kettle concentration of the catalyst at 3 mg / L, and the molar ratio of diethylaluminum chloride to the main catalyst at 750 to obtain the reaction glue.

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

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

[0120] Example 2:

[0121] Preparation process of E-POE2:

[0122] Raw material preparation: The cocatalyst is methylaluminoxane (MAO), the main catalyst is the catalyst with the structure shown in formula (III2), X = Y is Cl, M is Pd, the solvent in the solvent tank is petroleum ether, and the ethylene is polymerization-grade ethylene. The preparation process of the main catalyst is generally the same as that in Example 1 and will not be elaborated here.

[0123] Formula (III2)

[0124] Polymerization reaction: Mix petroleum ether and methylaluminoxane, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses a three-kettle series operation for continuous reaction, controlling the polymerization temperature at 60 °C, the pressure at 1.5 MPa, the ethylene flow rate at 10.0 kg / h, the residence time at 1.5 h, the single-kettle concentration of the catalyst at 2 mg / L, and the molar ratio of methylaluminoxane to the main catalyst at 1000 to obtain the reaction glue solution.

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

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

[0127] Example 3:

[0128] Preparation process of E-POE3:

[0129] Raw material preparation: The cocatalyst is sesquiethylaluminum, the main catalyst is the catalyst with the structure shown in formula (III3), X is Cl, Y is Me, M is Pd, the solvent in the solvent tank is n-heptane, and the ethylene is polymerization-grade ethylene. The preparation process of the main catalyst is generally the same as that in Example 1 and will not be elaborated here.

[0130] Formula (III3)

[0131] Polymerization reaction: Mix n-heptane and sesquiethylaluminum, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses a three-kettle series operation for continuous reaction, controlling the polymerization temperature at 55 °C, pressure at 1.8 MPa, ethylene flow rate at 8.0 kg / h, residence time at 1.5 h, the single-kettle concentration of the catalyst at 3 mg / L, and the molar ratio of sesquiethylaluminum to the main catalyst at 1500 to obtain the reaction glue solution.

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

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

[0134] Example 4:

[0135] Preparation process of E-POE4:

[0136] Raw material preparation: The cocatalyst is diethylaluminum chloride (DEAC), the main catalyst is the catalyst shown in the structure of formula (III4), X and Y are both Cl, M is Ni, the solvent in the solvent tank is n-heptane, and the ethylene is polymerization-grade ethylene. The preparation process of the main catalyst is generally the same as that in Example 1 and will not be elaborated here.

[0137] Formula (III4)

[0138] Polymerization reaction: Mix n-heptane and DEAC, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses a three-kettle series operation for continuous reaction, controlling the polymerization temperature at 50 °C, pressure at 2.0 MPa, ethylene flow rate at 10.0 kg / h, residence time at 1.5 h, the single-kettle concentration of the catalyst at 4 mg / L, and the molar ratio of DEAC to the main catalyst at 1000 to obtain the reaction glue solution.

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

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

[0141] Example 5:

[0142] Preparation process of E-POE5:

[0143] Raw material preparation: The cocatalyst is modified methylaluminoxane (MMAO), the main catalyst is the catalyst with the structure shown in formula (III5), X = Y is Br, M is Ni, the solvent in the solvent tank is toluene, and the ethylene is polymerization-grade ethylene. The preparation process of the main catalyst is generally the same as that in Example 1 and will not be elaborated here.

[0144] Formula (III5)

[0145] Polymerization reaction: Mix n-heptane with MMAO, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses three kettles in series for continuous reaction. Control the polymerization temperature at 50°C, the pressure at 1.5 MPa, the ethylene flow rate at 10.0 kg / h, the residence time at 2.0 h, the single-kettle concentration of the catalyst at 3 mg / L, and the molar ratio of MMAO to the main catalyst at 500.

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

[0147] The rubber solution after three-stage stripping and drying passes through an automatic filtering device, then is washed with water to lower the temperature, with the temperature controlled at 35°C, and then undergoes another filtering process. It enters an extrusion device for dehydration treatment. After extrusion dehydration, it is dried at a temperature of 90°C. The water content of the rubber particles is lower than 0.15%. The rubber particles enter a screw extruder, and are extruded and granulated through the screw. The screw rotation speed is 50 r / min, and the temperature is controlled at 110°C. Then it is automatically packaged to obtain E-POE5.

[0148] Example 6:

[0149] This Example 6 is generally the same as Example 1, except that the cocatalyst used is DEAC, and E-POE6 is obtained.

[0150] Example 7:

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

[0152] Example 8:

[0153] This Example 8 is generally the same as Example 3, except that the single-reactor concentration of the catalyst is 10 μg / L, and E-POE8 is obtained.

[0154] Example 9:

[0155] This Example 9 is generally the same as Example 4, except that the cocatalyst is sesquiethylaluminum, and E-POE9 is obtained.

[0156] Example 10:

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

[0158] Comparative Example 1:

[0159] The preparation process of Comparative Example 1 is generally the same as that of Example 1, except that the post-treatment process uses a dry deashing process. The specific dry deashing post-treatment process is as follows: The reaction glue solution enters a flash evaporation tank for flash evaporation to recover ethylene and solvent. The flash evaporation temperature is controlled at 110 °C, the pressure is controlled at 0.05 MPa, and the glue solution concentration is controlled at 30%. The polymer glue solution after flash evaporation is transferred to a refining deashing unit through a metering pump for deashing treatment of the glue solution, and the pressure difference of the refining tower is maintained below 7 MPa. The glue solution is transferred to a devolatilization granulation unit, and the dry deashing process used is preferably through primary, secondary, and multi-stage deashing under vacuum. Among them, the temperature of the primary deashing is controlled at 110 °C, and the rotation speed is 80 r / min; the temperature of the secondary deashing is controlled at 130 °C, and the rotation speed is 70 r / min; the temperature of the tertiary deashing is controlled at 170 °C, and the rotation speed is 30 r / min to prepare E-POE1'.

[0160] Comparative Example 2:

[0161] Preparation process of polyethylene particles:

[0162] Raw material preparation: The cocatalyst is diethylaluminum chloride, the main catalyst is a catalyst with the 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: Mix cyclohexane and diethylaluminum chloride, then mix with the main catalyst and enter the reaction kettle to react with ethylene. The reaction process uses a three-kettle series operation for continuous reaction, controlling the polymerization temperature at 40 °C, the pressure at 2.5 MPa, the ethylene flow rate at 12.5 kg / h, the residence time at 1.5 h, the single-kettle concentration of the catalyst at 3 mg / L, and the molar ratio of diethylaluminum chloride to the main catalyst at 750 to obtain a polyethylene slurry.

[0165] Post-treatment process: After filtering and drying the polyethylene slurry, polyethylene particles are obtained.

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

[0167] Table 2 Product indicators obtained from tests of examples and comparative examples

[0168]

[0169] From the comparison of Examples 1 to 10, it can be seen that the ash content and volatile content of the polyolefin elastomers prepared with main catalysts of different structures are both low, the purity is high, and they have good application prospects. The product prepared in Comparative Example 2 is polyethylene, which has good cleanliness, but has poor branching degree and elasticity, and it is difficult to be used as an elastomer. Moreover, the ash content and volatile content of the products prepared by the two methods of Comparative Example 1 and Comparative Example 2 are both high, the impurity content is high, and it is difficult to carry out further applications.

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

[0171] Table 3 Formulation for Photovoltaic Encapsulation Film

[0172]

[0173] Application Example 1:

[0174] Mix 100 parts of E-POE1 in Example 1, 6 parts of PE-grafted maleic anhydride resin, 0.1 part of silane coupling agent vinyltriethoxysilane, 0.1 part of crosslinking agent dicumyl peroxide, 0.15 part of antioxidant 2,6-di-tert-butyl-4-methylphenol, and 0.1 part of ultraviolet absorber 2-(2-hydroxy-5-methylphenyl)benzotriazole evenly, and granulate with a twin-screw extruder to prepare reinforced resin-modified E-POE pellets. The processing temperature is 130 °C, the film extrusion temperature is 110 °C, and the film thickness is 0.3 mm to prepare an E-POE film.

[0175] Application Example 2:

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

[0177] Application Example 3:

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

[0179] Application Example 4:

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

[0181] Application Example 5:

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

[0183] Comparative Application Example 1:

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

[0185] The properties of the films prepared in Application 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 light transmittance than the POE film, and its aging effect is equivalent 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 purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only specific embodiments of the present invention and is not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within 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 (II): Formula (II); Wherein, c1 and c3 are independently selected from substituted C1~C5 alkyl or phenoxy, there are 1 to 3 substituents on the C1~C5 alkyl, each of which is independently selected from any one of phenyl, thiophene, and furan, and at least one substituent is selected from thiophene, furan, or at least one of c1 and c3 is selected from phenoxy; c2 is selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl; R3 and R4 are independently selected from hydrogen, substituted or unsubstituted C1~C5 alkyl, C3~C 10 Any of the cycloalkyl groups; When there is a substituent on the substituted or unsubstituted C1~C5 alkyl group, the substituent is selected from any one of halogen and C1~C5 alkyl group.

2. The ligand compound according to claim 1, characterized in that R3 and R4 are independently selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl and cyclohexane.

3. A ligand compound, characterized in that The ligand compound has a structure shown in any one of formula (II1) to formula (II3): 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 (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 is 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 (IV): Formula (IV); Wherein, c1 and c3 are independently selected from substituted C1~C5 alkyl or phenoxy, there are 1 to 3 substituents on the C1~C5 alkyl, each of which is independently selected from any one of phenyl, thiophene, and furan, and at least one substituent is selected from thiophene, furan, or at least one of c1 and c3 is selected from phenoxy; c2 is selected from any one of hydrogen, substituted or unsubstituted C1~C5 alkyl; R3 and R4 are independently selected from hydrogen, substituted or unsubstituted C1~C5 alkyl, C3~C 10 Any of the cycloalkyl groups; When there is a substituent on the substituted or unsubstituted C1~C5 alkyl group, the substituent is selected from any one of halogen and C1~C5 alkyl; M is selected from any one of Ni and Pd; X and Y are each independently selected from any one of halogen and methyl.

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 (II) is subjected to a coordination reaction with a divalent metal compound to obtain a complex having a structure as shown in formula (IV); The divalent metal compound is at least one selected from ethylene glycol dimethyl ether nickel bromide, nickel chloride, nickel iodide, allyl nickel chloride, triphenylphosphine nickel chloride, palladium chloride, and alkyl palladium chloride; Formula (II); Wherein, c1, c2, c3, R3, and R4 are as described in claim 6.

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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