CN115260357A - Copolymerization method of spherical or spheroidal copolymer of olefin-terminal alkenylsilane/siloxane and copolymer - Google Patents

Copolymerization method of spherical or spheroidal copolymer of olefin-terminal alkenylsilane/siloxane and copolymer Download PDF

Info

Publication number
CN115260357A
CN115260357A CN202110473860.7A CN202110473860A CN115260357A CN 115260357 A CN115260357 A CN 115260357A CN 202110473860 A CN202110473860 A CN 202110473860A CN 115260357 A CN115260357 A CN 115260357A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
formula
alkyl
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110473860.7A
Other languages
Chinese (zh)
Other versions
CN115260357B (en
Inventor
高榕
苟清强
赖菁菁
李昕阳
安京燕
马冬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202110473860.7A priority Critical patent/CN115260357B/en
Publication of CN115260357A publication Critical patent/CN115260357A/en
Application granted granted Critical
Publication of CN115260357B publication Critical patent/CN115260357B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)

Abstract

The invention discloses a method for copolymerizing a spherical or spheroidal copolymer of olefin-terminal alkenyl silane/siloxane and the copolymer obtained by the method. The copolymerization method comprises the steps of contacting an olefin and terminal alkenyl silane/siloxane shown in a formula (1) or derivatives thereof with a catalyst for reaction in the presence of an alkane solvent,
Figure DDA0003046376590000011
according to the invention, through selecting the reacted terminal alkenyl silane/siloxane monomer, the catalyst and a proper polymerization process, the spherical and/or quasi-spherical polymer with a good form is directly prepared without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.

Description

Copolymerization method of spherical or spheroidal copolymer of olefin-terminal alkenylsilane/siloxane and copolymer
Technical Field
The invention relates to the field of preparation of high molecular polymers, in particular to a copolymerization method of a spherical or spheroidal copolymer of olefin-terminal alkenyl silane/siloxane and the copolymer obtained by the copolymerization method.
Background
The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the original excellent physical and chemical properties of the polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, the printing property, the wettability and the compatibility with other materials can be improved, and new characteristics which are not possessed by raw materials are endowed. High pressure free radical polymerization is currently used commercially to promote direct copolymerization of olefins with polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymers. Although the polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
The olefin copolymers containing vinylsilane or siloxane derivative groups can be used in a variety of applications, for example as various types of cable materials, pipes, adhesives, gaskets and crosslinked foams. Vinyl silane-based groups can be linked to olefin polymers by two methods: one method is to copolymerize olefin and vinyl silane compound at high temperature and high pressure under the catalysis of free radical initiator (such as US 3225018), the polymerization process is similar to the high-pressure homopolymerization of ethylene, and the structure of the obtained copolymer is similar to that of low-density polyethylene; another method is to graft an allyl or vinyl silane onto an existing polyolefin (e.g.US 3646155), which has the advantage that both low density polyethylene and high density polyethylene can be grafted, but has the disadvantage that the grafting requires the additional use of free-radical initiators, which also complicates the preparation process. In addition, too little free radical initiator can result in too low a graft; too much free radical initiator may result in excessive crosslinking of the polymer. If ethylene can be catalyzed to coordinate with the terminal alkenylsilane/siloxane groups, the polymerization process can be simplified and the content of terminal alkenylsilane/siloxane groups in the polymer chain can be controlled.
Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins with silicon-containing polar monomers (terminal alkenylsilanes/siloxanes). For example, WO 03/044066 A2 discloses that ethylene can be copolymerized with allyl-or vinyl-silanes using late transition metal complexes of bidentate or tridentate ligands, however, this process requires the use of expensive Modified Methylaluminoxane (MMAO) as cocatalyst and polymerises at higher ethylene polymerisation pressures of 4.0 to 6.0MPa, resulting in polymers with lower molecular weight and branching. 20745-20752 adopts pyridine diimine iron series catalyst to catalyze propylene and polar monomer containing silicon for copolymerization, the method still needs MMAO as cocatalyst, needs polymerization reaction for 16 hours at 30 ℃ or even lower temperature and 0 ℃ and has lower polymerization activity. And the catalyst is not loaded, when the catalyst catalyzes the copolymerization of olefin and polar monomer, the obtained polymer is easily in a viscous blocky solid and is easily scaled in polymerization equipment, thereby bringing difficulties to the transportation, solvent removal, granulation and the like of the polymer.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention provides a spherical or spheroidal polar polyolefin with silane or siloxane groups and a higher melting point, which can introduce crosslinkable silane or siloxane polar groups and retain the chain rigidity.
An object of the present invention is to provide a method for copolymerizing an olefin-terminal alkenylsilane/siloxane spherical or spheroidal copolymer comprising contacting an olefin and a terminal alkenylsilane/siloxane represented by the formula (1) or a derivative thereof with a catalyst in the presence of an alkane solvent to react and obtain the copolymer,
Figure BDA0003046376570000021
in the formula (1), L1-L3Independently selected from H, C with or without substituent1-C30Alkyl radical, L4Is C containing substituents1-C30Alkylene, R'1-R’3Is halogen, C with or without substituents1-C10Alkyl, C with or without substituents1-C10An alkoxy group.
Preferably, L1And L2Are all H.
Preferably, L3Is H, C1-C20Substituted or unsubstituted alkyl; more preferably, L3Is H, C1-C10Alkyl or C1-C10An alkyl haloalkyl group; most preferably, L3Is H or C1-C6An alkyl group.
Preferably, L4Is C containing substituents1-C20Alkylene, more preferably, L4Is C containing substituents1-C10An alkylene group. Such as L4Is methylene containing substituent, ethylene containing substituent, propylene containing substituent, butylene containing substituent, C containing substituent5Alkylene group, C containing substituent6Alkylene group, C containing substituent7Alkylene group, C containing substituent8Alkylene group, C containing substituent9Alkylene group, C containing substituent10Alkylene group, C containing substituent12Alkylene group, C containing substituent14Alkylene group, C containing substituent18Alkylene group, C containing substituent20An alkylene group.
Preferably, in the formula (1), L1-L4Wherein said substituents are selected from halogen, C6-C10Aryl radical, C1-C20Alkyl radical, C1-C20Alkoxy, hydroxy, ester, preferably from halogen, phenyl, C1-C6Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C1-C10Alkoxy, hydroxyl, ester group.
The carbon number of the alkylene group means the number of C's in the linear chain, not including the number of C's in the side group, e.g., isopropylidene (-CH)2-CH(CH3) -) is referred to herein as C with a pendant group (methyl)2An alkylene group.
In the present invention, the "terminal alkenyl group" includes a vinyl group and an α -alkenyl group, and the double bond in the group is located at one end of the molecular chain. "terminal alkenylsilane/siloxane" refers to "terminal alkenylsilane" and/or "terminal alkenylsiloxane".
According to a preferred embodiment of the present invention, specific examples of the terminal alkenylsilane/siloxane include, but are not limited to, trimethyl (1-methyl-2-propen-1-yl) silane, trimethyl (1-methyl-3-buten-1-yl) silane, (1-ethyl-2-propen-1-yl) trimethylsilane, trimethyl (1, 2-tetramethyl-3-buten-1-yl) silane, [1- (trimethylsilyl) -3-buten-1-yl ] benzene, methoxydimethyl (1-methyl-2-propen-1-yl) silane, 2- (trimethylsilyl) -4-penten-1-ol, vinyldimethyl (1-methylethyl) silane, (chloromethyl) dimethyl-2-propen-1-yl silane, hexyldimethyl-2-propen-1-yl silane, dichlorohexyl-2-propen-1-yl-silane, dichloro-5-hexen-1-ylmethylsilane, (dimethyl (1-methyl-2-propen-1-yl) silane, 5-yl-1-methyl-hexen-1-yl-trimethylsilyl, triethylsilyltrimethyl-4-hexenyl) silane, diethylmethyl (2-methyl-3-buten-1-yl) silane, methoxydimethyl (1-methyl-2-propen-1-yl) silane, 1-vinyl-3- (trimethylsilyl) cyclopentane, chlorodimethyl (1-methyl-2-propen-1-yl) silane, 3-buten-1-ylmethoxydimethylsilane, 3-buten-1-ylchlorodimethylsilane, allyl-t-butyldimethylsilane, trichloro-10-undecen-1-yl silane, (7-oct-1-yl) trimethoxysilane, dimethoxymethyl-2-propen-1-yl silane, 7-octen-2-ol-2-methyl-4- (trimethylsilyl), (1, 1-dimethylethyl) dimethyl [ (1-methyl-2-propen-1-yl) oxy ] silane, 1- (trimethylsilyl) -4-penten-1-ol, 5- (trimethylsilyl) -1-penten-3-ol, 3- (3-buten-1-yldimethylsilyl) -1-propanol, 1- (trimethylsilyl) -3-propen-1-2-propen-1-yl-ol, 1- (trimethylsilyl) -1-propen-1-2-1-yl) alcohol, 1- (dimethyl-2-propen-1-ylsilyl) -2-propanol, methyl 3-trimethylsilyl-4-pentenoate, methyl 2-propenoate (trimethylsilyl) ester, triethoxy (2-methyl-3-buten-1-yl) silane, and the like.
According to preferred embodiments of the present invention, the olefin comprises an olefin having from 2 to 16 carbon atoms, and in some embodiments of the present invention, the olefin comprises ethylene or an alpha-olefin having from 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C2-C10Alpha-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like.
The catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from at least one of metal complexes shown in a formula (I),
Figure BDA0003046376570000031
in the formula (I), R1、R2Independently selected from C containing or not containing substituents1-C30A hydrocarbyl group; r3、R4Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Hydrocarbyl radical, adjacent R3And R4Optionally linked to each other to form a ring or ring system; r' is selected from C containing substituent or not containing substituent1-C20A hydrocarbyl group; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C containing substituent or not containing substituent1-C10Hydrocarbyl, substituted or unsubstituted C1-C10A hydrocarbyloxy group.
According to some embodiments of the metal complex of the present invention, in formula (I), R1、R2Independently selected from C containing or not containing substituents1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, preferably, R1、R2Is a group of formula (II):
Figure BDA0003046376570000041
in the formula (II), R1～R5The same or different, each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20An alkaryl group; r1～R5Optionally linked to each other to form a ring or ring system;
preferably, in formula (II), R1～R5Each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C2-C10Alkenyloxy, substituted or unsubstituted C2-C10Alkynyloxy, substituted or unsubstituted C3-C10Cycloalkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C7-C15Aralkyl, substituted or unsubstituted C7-C15An alkaryl group.
According to some embodiments of the metal complex of the present invention, in formula (I), M is selected from nickel or palladium.
According to some embodiments of the metal complex of the present invention, in formula (I), Y is selected from O or S;
according to some embodiments of the metal complex of the present invention, in formula (I), X is selected from the group consisting of halogen, C with or without substituent1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, preferably selected from halogen, C with or without substituents1-C6Alkyl, substituted or unsubstituted C1-C6An alkoxy group.
According to some embodiments of the metal complex of the present invention, in formula (I), R' is selected from C optionally having a substituent1-C20Alkyl, preferably C, optionally substituted1-C10Alkyl, more preferably C with or without substituent1-C6An alkyl group.
According to some embodiments of the metal complex of the present invention, in formula (I), R3And R4The same or different, each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstitutedC of (A)6-C20Aryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20An alkaryl group.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (IX):
Figure BDA0003046376570000051
in the formula (IX), R1～R5Each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C3-C10Cycloalkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C7-C15Aralkyl, substituted or unsubstituted C7-C15An alkaryl group;
R3、R4independently selected from hydrogen, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10Alkoxy, halogen, preferably independently selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl radical, C1-C6Alkoxy, halogenated C1-C6Alkoxy, halogen;
m is nickel; y is O; x is selected from fluorine, chlorine and bromine;
r' is selected from C containing substituent or not containing substituent1-C20Alkyl, preferably C, optionally substituted1-C10Alkyl, more preferably C with or without substituent1-C6An alkyl group.
The metal complex shown as the formula (I) can be prepared into a general formulaThe preparation method comprises the following steps: reacting a diimine compound of the formula (A) with MXnAnd R' YH, in the presence of a catalyst,
Figure BDA0003046376570000061
in the formula (A), R1、R2、R3And R4Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same meanings as in formula (I).
The reaction is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is selected from one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of from 15 to 40 ℃.
The MXn comprises a nickel halide, such as nickel bromide or nickel chloride; and 1, 2-dimethoxyethane nickel halides, such as 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.
The structure and preparation method of the metal complex shown in the formula (I) or the formula (IX) can be found in the chinese patent application CN201911049039.1, and the text of the chinese patent application CN201911049039.1 is introduced into the present invention.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (III):
Figure BDA0003046376570000062
in the formula (III), R5～R8Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30Hydrocarbyl radical, R5～R8Optionally linked to each other to form a ring or ring system; preferably, R5～R8Independently selected from hydrogen, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10Alkoxy, halogen.
In the formula (III), R1、R2Same or different and independently selected from C containing substituent or not containing substituent1-C30A hydrocarbyl group; r' is selected from C containing substituent or not containing substituent1-C20A hydrocarbyl group; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C containing substituent or not containing substituent1-C10Hydrocarbyl, substituted or unsubstituted C1-C10A hydrocarbyloxy group.
According to some embodiments of the metal complex of the present invention, in formula (III), R1、R2Independently selected from C containing or not containing substituents1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, preferably, R1、R2Is a group represented by the above formula (II).
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (IV):
Figure BDA0003046376570000071
in the formula (IV), R1～R11Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstitutedC of (A)6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
Preferably, R1～R11Independently selected from hydrogen, halogen, hydroxyl, C containing substituent or not containing substituent1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C2-C10Alkenyloxy, substituted or unsubstituted C2-C10Alkynyloxy, substituted or unsubstituted C3-C10Cycloalkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C7-C15Aralkyl and substituted or unsubstituted C7-C15An alkaryl group.
The metal complex as shown in formula (III) can be prepared by the following steps: reacting a diimine compound represented by the formula (B) with MXn and R' YH,
Figure BDA0003046376570000072
Figure BDA0003046376570000081
in the formula (B), R5～R8Have the same definition as formula (III); r1And R2Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), and n is a group satisfying the valence of MThe number of X states, n is 1,2 or 3; y and R 'in R' YH have the same definition as that of formula (I).
The above reaction to produce the metal complex represented by the formula (III) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from the group consisting of dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of from 15 to 40 ℃.
The MXn comprises a nickel halide, such as nickel bromide or nickel chloride; and 1, 2-dimethoxyethane nickel halides, such as 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound of the formula (B) comprises reacting a diketone compound of the formula (B') with R1NH2And R2NH2And reacting to produce the diimine compound represented by the formula (B).
Figure BDA0003046376570000082
In the above reaction to produce the diimine compound represented by formula (B), the reaction is carried out in the presence of an alkylaluminum and an aprotic solvent, preferably, the aprotic solvent is one or more of toluene, benzene, and xylene. The alkyl aluminum compound is C1-C6Alkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, etc., preferably trimethyl aluminum.
The related structure and preparation method of the metal complex shown in the formula (III) or the formula (IV) can be found in chinese patent application CN201911048975.0, which is incorporated herein in its entirety.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (V):
Figure BDA0003046376570000083
in the formula (V), R5～R7Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30Hydrocarbyl radical, R5～R7Optionally linked to each other to form a ring or ring system; preferably, R5～R7Independently selected from hydrogen, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10Alkoxy, halogen, more preferably selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl radical, C1-C6Alkoxy, halogenated C1-C6Alkoxy, halogen.
In the formula (V), R1、R2Same or different and independently selected from C containing substituent or not containing substituent1-C30A hydrocarbyl group; r' is selected from C containing substituent or not containing substituent1-C20A hydrocarbyl group; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C containing substituent or not containing substituent1-C10Hydrocarbyl, substituted or unsubstituted C1-C10A hydrocarbyloxy group.
According to some embodiments of the metal complex of the present invention, in formula (V), R1、R2Independently selected from C containing or not containing substituents1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, preferably, R1、R2Is a group of the formula (II) as defined above.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (VI):
Figure BDA0003046376570000091
in the formula (VI), R1～R5Independently selected from hydrogen, halogen, C containing substituent or not containing substituent1-C6Alkyl, substituted or unsubstituted C1-C6An alkoxy group; r is5～R10Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6An alkoxy group; m is nickel; y is O; x is selected from halogen; r' is selected from C containing substituent or not containing substituent1-C6An alkyl group.
The metal complex of formula (V) is prepared by the following steps: reacting a diimine compound of the formula (C) with MXnAnd R' YH, in the presence of a catalyst,
Figure BDA0003046376570000092
in the formula (C), R5、R6、R7Have the same definition as formula (V); r is1And R2Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same meanings as in formula (I).
The above reaction to produce the metal complex of formula (V) is carried out in an organic solvent, preferably the organic solvent is a haloalkane, more preferably the organic solvent is selected from one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of from 15 to 40 ℃.
The MXn comprises a nickel halide, such as nickel bromide or nickel chloride; and 1, 2-dimethoxyethane nickel halides, such as 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound of formula (C) comprises reacting a diketone compound of formula (C') with R1NH2And R2NH2And reacting to produce the diimine compound represented by the formula (C).
Figure BDA0003046376570000101
Wherein R is1、R2、R5-R7Have the same definition as formula (V).
In the above reaction for producing the diimine compound represented by (C), the catalyst used in the reaction is selected from organic acids such as formic acid, acetic acid, and p-toluenesulfonic acid, and the solvent is preferably one or more selected from methanol, ethanol, and acetonitrile.
The structure and preparation method of the metal complex shown in the formula (V) or formula (VI) can be found in chinese patent application CN201911049899.5, which is incorporated herein in its entirety.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (VII):
Figure BDA0003046376570000102
in the formula (VII), R21～R24Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Hydrocarbyl, substituted or unsubstituted C1-C20Hydrocarbyloxy radicals, R21～R24Optionally linked to each other to form a ring or ring system; preferably, R21～R24Each independently selected from hydrogen, halogen, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
In the formula (VII), R1、R2Same or different and independently selected from C containing substituent or not containing substituent1-C30A hydrocarbyl group; r' is selected from C containing substituent or not containing substituent1-C20A hydrocarbyl group; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C containing substituent or not containing substituent1-C10Hydrocarbyl and optionally substituted C1-C10A hydrocarbyloxy group.
According to some embodiments of the metal complex of the present invention, in formula (VII), R1、R2Independently selected from C containing or not containing substituents1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, preferably, R1、R2Is a group of the formula (II) as defined above.
According to some embodiments of the metal complex of the present invention, the metal complex has a structure as shown in formula (VIII):
Figure BDA0003046376570000111
in the formula (VIII), R1～R10Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted orC without substituents6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
The metal complex represented by the formula (VII) is prepared by the following steps: reacting a diimine compound of the formula (D) with MXnAnd R' YH, in the presence of a catalyst,
Figure BDA0003046376570000121
in the formula (D), R21～R24Has the same definition as formula (VII); r1、R2Has the same definition as formula (I), MXnWherein M and X have the same definition as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as that of formula (I).
The above reaction to produce the metal complex represented by the formula (VII) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from the group consisting of dichloromethane, trichloromethane and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of from 15 to 40 ℃.
The MXn comprises a nickel halide, such as nickel bromide or nickel chloride; and 1, 2-dimethoxyethane nickel halides, such as 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound of formula (D) comprises reacting a diketone compound of formula (D') with R1NH2And R2NH2And reacting to produce the diimine compound represented by the formula (D).
Figure BDA0003046376570000122
In the above reaction for producing the diimine compound represented by formula (D), p-toluenesulfonic acid and an aprotic solvent are reacted in the presence, and the aprotic solvent is preferably one or more of toluene, benzene and xylene.
The related structure and preparation method of the metal complex shown in the formula (VII) or the formula (VIII) can be seen in Chinese patent application CN201911049898.0, and the Chinese patent application CN201911049898.0 is fully introduced into the invention.
In some embodiments of the present invention, in the above-described metal complexes, the substituents are selected from halogen, hydroxy, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10An alkoxy group; the substituents are preferably selected from halogen, hydroxy, C1-C6Alkyl, halogenated C1-C6Alkyl radical, C1-C6Alkoxy, halogenated C1-C6An alkoxy group.
In some embodiments, the C is1-C6The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3-dimethylbutyl, and the like.
In some embodiments, the C is1-C6The alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy, and the like.
In the above technical solution, preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
The cocatalyst is selected from an organic aluminum compound and/or an organic boron compound; wherein the organic aluminum compound is at least one of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide, and the organic boron compound is aryl boron and/or borate.
According to a preferred embodiment of the present invention, the organoaluminum compoundSelected from alkylaluminoxane or AlRnX1 3-nOf (a) an organoaluminum compound (aluminum alkyl or aluminum alkyl halide), of the general formula AlRnX1 3-nIn the formula, R is H or C1-C20Saturated or unsaturated hydrocarbon groups of (C)1-C20Saturated or unsaturated hydrocarbyloxy radicals, preferably C1-C20Alkyl radical, C1-C20Alkoxy radical, C7-C20Aralkyl or C6-C20An aryl group; x1Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, the concentration of the metal complex procatalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5mmol/L.
According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the procatalyst metal complex is (10 to 10000000): 1, for example, 10.
When the co-catalyst comprises an organoboron compound and an organoaluminum compound, the molar ratio of boron in the organoboron compound to the metal complex M in the main catalyst is (0.1 to 1000) 1, for example, 0.1; the molar ratio of aluminum in the organic aluminum compound to the metal complex M in the main catalyst is (10-10)5) 1, for example, 10.
According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent selected from C3-C20One or more alkanes, preferably selected from C3-C10The alkane, for example, may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.
According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.
According to a preferred embodiment of the invention, the conditions of the reaction include: the reaction temperature is-50 to 80 ℃, preferably-20 to 60 ℃, more preferably 10 to 60 ℃, for example, -40 ℃, -30 ℃, -20 ℃, -10 ℃,0 ℃,10 ℃,20 ℃,30 ℃,40 ℃,50 ℃, 70 ℃, 80 ℃ and any value therebetween; the reaction time is 10 to 200min, preferably 20 to 60min.
In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to a coordination copolymerization reaction. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process.
In the present invention, the "reaction system" refers to the whole formed by solvent, olefin, terminal alkenyl silane/siloxane or their derivative polar monomer, and catalyst.
The average particle diameter of the spherical or spheroidal copolymer obtained by the copolymerization method is 0.02-50.0 mm, and preferably 0.2-20.0 mm.
The method provided by the invention can directly obtain the spherical and/or spheroidal copolymer without subsequent processing such as granulation and the like, and the polymer has good appearance, so the method has good industrial application prospect.
It is a further object of the present invention to provide olefin-terminal alkenylsilane/siloxane copolymers comprising spherical and/or spheroidal polymers, obtainable by the above-described preparation process.
According to a preferred embodiment of the invention, at least part of the spherical and/or spheroidal polymers in the copolymer have a hollow structure.
According to a preferred embodiment of the present invention, the olefin-terminal alkenylsilane/siloxane copolymer comprises structural units derived from an olefin and structural units derived from a terminal alkenylsilane/siloxane represented by formula (2),
Figure BDA0003046376570000151
in the formula (2), L1-L3Each independently selected from H, C with or without substituent1-C30Alkyl radical, L4Is C containing substituents1-C30Alkylene, R'1-R’3Is halogen, C with or without substituents1-C10Alkyl, C with or without substituents1-C10An alkoxy group.
According to a preferred embodiment of the present invention, in formula (2), L1And L2Is H, L3Is H, C with or without substituents1-C20Alkyl radical, L4Is C containing substituents1-C20An alkylene group.
According to a preferred embodiment of the present invention, in formula (2), L1And L2Is H, L3Is H or C1-C6An alkyl group; l is4Is C containing a substituent1-C10Alkylene, the substituent is selected from halogen and C6-C10Aryl radical, C1-C20Alkyl radical, C1-C20Alkoxy, hydroxy, ester, preferably from halogen, phenyl, C1-C6Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C1-C10One or more of alkoxy, hydroxyl and ester group.
According to a preferred embodiment of the present invention, in the olefin-terminal alkenylsilane/siloxane copolymer, the content of the structural unit represented by formula (2) is 0.2 to 10.0mol%, and for example, may be 0.2mol%, 0.4mol%, 0.6mol%, 0.8mol%, 1.0mol%, 1.5mol%, 2.0mol%, 3.0mol%, 4.0mol%, 5.0mol%, 6.0mol%, 7.0mol%, 8.0mol%, 9.0mol%, 10.0mol%, and any value therebetween, and preferably 0.5 to 5.0mol%.
According to a preferred embodiment of the invention, said structural units derived from olefins comprise units derived from C2-C16Structural units of olefins, preferably derived from C2-C16Alpha-olefins or C3-C16Structural units of cycloolefins.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymer has a density of 0.3000 to 0.8500g/cm3For example, it may be 0.3000g/cm3、0.3500g/cm3、0.4000g/cm3、0.4500g/cm3、0.5000g/cm3、0.5500g/cm3、0.6000g/cm3、0.6500g/cm3、0.7000g/cm3、0.7500g/cm3、0.8000g/cm3、0.8500g/cm3And any value therebetween, preferably 0.4000 to 0.7500g/cm3The density is measured by the method in GB/T6343-2009.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymer has an average particle size of 0.02 to 50.0mm, and may for example be 0.02mm, 0.05mm, 0.1mm, 0.5mm, 1.0mm, 1.5mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.2 to 20.0mm.
According to a preferred embodiment of the present invention, the wall thickness of the spherical and/or spheroidal polymer having a hollow structure is 1 to 95% of the radius of the spherical and/or spheroidal polymer, for example 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95% and any value therebetween, preferably 5 to 70%, more preferably 10 to 50%.
According to a preferred embodiment of the present invention, the melting point of the olefin-terminal alkenylsilane/siloxane copolymer is 70 to 125 ℃, for example 70 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, 105 ℃, 110 ℃, 120 ℃, 125 ℃ and any value in between.
According to a preferred embodiment of the invention, the weight average molecular weight of the olefin-terminal alkenylsilane/siloxane copolymer is from 5,000 to 500,000, preferably from 10,000 to 300,000.
According to a preferred embodiment of the invention, the olefin-terminal alkenylsilane/siloxane copolymer has a molecular weight distribution of 4.5 or less, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 and any value in between, preferably a molecular weight distribution of 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
The invention also aims to provide the application of the copolymer obtained by the copolymerization method in the preparation of polyolefin materials.
Symbols such as R used in different formulae or structural formulae herein1～R8、R21～R24、R1～R11、R’、X、M、Y、L1-L4、R’1-R’3And the like, unless otherwise specified, have the same definition in each general formula or structural formula.
In the present invention, alkyl means straight-chain alkyl, branched-chain alkyl or cycloalkyl. E.g. C1-C20Alkyl is C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl or C3-C20A cycloalkyl group. Examples of linear or branched alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
C3-C20Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6-C20Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.
Alkenyl refers to straight chain alkenyl, branched chain alkenyl or cycloalkenyl. E.g. C2-C20Alkenyl means C1-C20Linear alkenyl of (A), C3-C20Branched alkenyl or C3-C20The cycloalkenyl group of (1). Examples of alkenyl groups include, but are not limited to: vinyl, allyl, butenyl.
C7-C20Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.
C7-C20Examples of alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.
The process for preparing olefin-terminal alkenylsilane/siloxane copolymers provided by the present invention uses a novel trinuclear metal complex-containing catalyst.
A polymerization method capable of directly preparing spherical polyolefin is found by screening a catalyst structure, polymerization conditions and terminal alkenylsilane/siloxane monomers. The catalyst does not need to be loaded to directly prepare the polyolefin with silane or siloxane, so that the complicated loading process of the catalyst can be avoided, the spherical particles can be directly prepared, the post-processing procedure of polymer granulation can be avoided, and great convenience is brought to the industrial production of the method.
Furthermore, in the preparation method of the olefin-terminal alkenylsilane/siloxane copolymer provided by the invention, by selecting the reacted terminal alkenylsilane/siloxane monomer, the catalyst and a proper polymerization process, the spherical and/or spheroidal polymer with good form is directly prepared without subsequent processing steps such as granulation, and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.
Drawings
FIG. 1 is a photograph of the copolymer obtained in example 7.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The analytical characterization instrument used in the present invention was as follows:
the polymer is washed with dilute acid solution before measurement to make the metal content in the polymer less than or equal to 50ppm.
1. Nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz), tetramethylsilicon (TMS) as an internal standard, was used to test the structure of the complex ligands at 25 ℃.
2. Comonomer content of the polymer: wavelength dispersive X-ray fluorescence spectroscopy (XRF): the composition of elements in a polymer sample is qualitatively determined according to an X-ray fluorescence spectrum by using a wavelength dispersion X-ray fluorescence spectrometer of Axios-Advanced type of PANalytical, the Netherlands, and the content of the elements in the polymer is semi-quantitatively determined according to the peak intensity of the elements in the X-ray fluorescence spectrum.
2. Molecular weight and molecular weight distribution of polymer PDI (PDI = Mw/Mn): using PL-GPC220, in trichlorobenzene at 150 ℃ as solvent (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 1 um M1 XED-B300X 7.5 nm).
3. Method of activity measurement: gravimetric method. The activity is expressed as polymer weight (g) × 60/(nickel (mol) × reaction time (min)).
4. Polymer Density test: the density was measured using GB/T6343-2009.
Example 1
Figure BDA0003046376570000181
Complex Ni1Preparation of
The mixture containing 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.175g (0.6 mmol) of ligand L1, and stirred at room temperature for 6 hours, followed by precipitation with anhydrous ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain yellow powdery solid Ni1. Yield: 70.2 percent. Elemental analysis (C)44H58Br6N4Ni3O2): c,39.72; h,4.39; n,4.21; experimental values (%): c,39.38; h,4.60; and N,3.96.
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were poured into the polymerization system3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of N, N-dimethylbenzeneAmmonium tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added1The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 3.34X 106g·mol-1(Ni)·h-1The weight average molecular weight was 16.7 ten thousand, the molecular weight distribution was 3.26, and the molar content of Si monomer was 3.45%. The average particle size of the spheroidal polymer was 0.78mm.
Example 2
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2h, evacuated while hot and purged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 124. Mu.L of AliBu3(95％)，50μL AlMe3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni were added1The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 4.23X 106g·mol-1(Ni)·h-1Weight average molecular weight is 16.4 ten thousand, molecular weight distribution is 3.42, and Si monomer molar content is 3.50%. The average particle size of the spheroidal polymer was 0.68mm.
Example 3
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2hrs, evacuated while hot and purged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added1. The reaction was vigorously stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with polymerization activity of1.96×106g·mol-1(Ni)·h-1Weight average molecular weight was 8.2 ten thousand, molecular weight distribution was 4.14, and molar content of si monomer was 3.01%. The average particle size of the spheroidal polymer was 0.72mm.
Example 4
Figure BDA0003046376570000191
Complex Ni2Preparation of
Will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.272g (0.6 mmol) of ligand L2. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni2. The yield was 74.1%. Elemental analysis (C)64H62Br6F4N4Ni3O2): c,46.57; h,3.79; n,3.39; experimental values (%): c,46.72; h,3.97; and N,3.48.
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2h, evacuated while hot and purged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlMe were charged to the polymerization system3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate, while adding 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni2The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 1.96X 106g·mol-1(Ni)·h-1The weight average molecular weight was 12.6 ten thousand, the molecular weight distribution was 4.43, and the molar content of the Si monomer was 3.01%. The average particle size of the spheroidal polymer was 0.70mm.
Comparative example 1
Comparative example 1 differs from example 3 in that: the amount of the comparative catalyst A (shown in formula (I')) was 0.025. Mu. Mol.
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2h, evacuated while hot and purged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, and 25. Mu.L of MAO (1.53 mol/L in toluene) were poured into the polymerization system, 25.0. Mu.L (1.0 mmol/L in toluene) of complex A was added, and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 1.04X 106g·mol-1(Ni)·h-1The weight average molecular weight was 6.8 ten thousand, the molecular weight distribution was 3.82, and the molar content of Si monomer was 2.06%.
Figure BDA0003046376570000201
Example 5
1) Ligand L3The preparation of (1):
under the protection of nitrogen, 2,4, 6-trimethylaniline (1.7mL, 12mmol) was dissolved in 20mL of toluene, 12mL of trimethylaluminum (1.0M, 12mmol) was added dropwise at room temperature, the reaction was refluxed for 2 hours, the system was cooled to room temperature, camphorquinone (0.831g, 5mmol) was added, and the system was refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and performing column chromatography to obtain yellow ligand L3The yield is 62.5 percent.1HNMR(300MHz,CDCl3),δ(ppm)[an isomer ratio of 1.2:1]:major isomer:6.72(s,4H,Ar-H),2.26-2.13(m,12H,CAr-CH3),1.87(s,6H,CAr-CH3),1.79(m,4H,CH2),1.42(m,1H),1.26(s,3H,CH3),1.07(s,6H,CH3)。Minor isomer:6.67(s,4H,Ar-H),2.09-2.01(m,12H,CAr-CH3),1.85(s,6H,CAr-CH3),1.79(m,4H,CH2),1.40(m,1H),1.26(s,3H,CH3),0.94(s,6H,CH3)。
2) Complex Ni3(R in the formula IV)1-R3Is methyl, R4-R7、R10Is hydrogen, R8、R9And R11Methyl, R' is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.240g (0.6 mmol) of the ligand L3Dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni3. The yield was 78.6%. Elemental analysis (C)60H82Br6N4Ni3O2): c,46.59; h,5.34; n,3.62; experimental values (%): c,46.24; h,5.67; and N,3.21.
3) Polymerization:
continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 62. Mu.L of AliBu3 (95%), 50. Mu.L of AlMe3 (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni complex was added3The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 5.42X 106g·mol-1(Ni)·h-1The weight average molecular weight was 9.33 ten thousand, the molecular weight distribution was 3.54, and the molar content of Si monomer was 4.85%. The average particle size of the spheroidal polymer was 0.69mm.
Example 6
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was dried continuously at 130 ℃ for 2hrs, evacuated while hot and charged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt3(0.1 mol/L in heptane), 12.5. Mu.L (0.01)mol/L toluene solution) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L toluene solution) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L toluene solution) of complex Ni was added3. The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with polymerization activity of 3.72 × 106g·mol-1(Ni)·h-1The weight average molecular weight was 7.26 ten thousand, the molecular weight distribution was 3.49, and the molar content of Si monomer was 4.76%. The average particle size of the spheroidal polymer was 0.77mm.
Example 7
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 450mL of hexane, 5mL (24.1 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 6.2mL of AliBu3 (95%), 0.5mL of AlMe3 (1.0 mol/L in heptane), 6.4mg (12.5. Mu. Mol) of tris (pentafluorophenyl) borane, 11.5mg (12.5. Mu. Mol) of triphenylmethyl tetrakis (pentafluorophenyl) borate were charged into the polymerization system, and 1.9mg (1.25. Mu. Mol) of the complex Ni was added2The reaction was carried out at 20 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 7.82X 106g·mol-1(Ni)·h-1The weight average molecular weight was 18.72 ten thousand, the molecular weight distribution was 3.42, and the molar content of Si monomer was 4.47%. The average particle diameter mm of the spheroidal polymer in the copolymer was 3.2mm, and the density of the resulting polymer was 0.5724g/cm3。
Comparative example 2
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2h, evacuated while hot and purged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L in toluene) were charged into the polymerization system, and 12.5. Mu.L (1.0 mmol/L in toluene) of Ni complex was added3The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 2.56X 106g·mol-1(Ni)·h-1Weight averageThe molecular weight is 7.42 ten thousand, the molecular weight distribution is 3.73, and the molar content of Si monomer is 3.34%. The resulting polymer had no spherical particles.
Example 8
1) Ligand L4The preparation of (1):
under the protection of nitrogen, 2, 6-dimethyl-4-bromo-aniline (2.45g, 12mmol) was dissolved in 20mL of toluene, 12mL (1.0M, 12mmol) of trimethylaluminum was added dropwise at room temperature, the reaction was refluxed for 2 hours, the system was cooled to room temperature, camphorquinone (0.831g, 5mmol) was added, and the system was refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and performing column chromatography to obtain yellow ligand L4The yield is 60.7%.1HNMR(300MHz,CDCl3),δ(ppm)[an isomer ratio of 1.1:1]:major isomer:7.05(s,4H,Ar-H),2.18(m,12H,CAr-CH3),1.85(m,4H,CH2),1.37(m,1H),1.26(s,3H,CH3),1.06(s,6H,CH3).Minor isomer:7.02(s,4H,Ar-H),2.04(m,12H,CAr-CH3),1.85(m,4H,CH2),1.37(m,1H),1.26(s,3H,CH3),0.96(s,6H,CH3)。
2) Complex Ni4(R in the structural formula IV)1、R3Is methyl, R2Is bromine, R4-R7、R10Is hydrogen, R8、R9And R11Methyl, R' is ethyl, M is nickel, Y is O, X is Br):
a mixture containing 0.278g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.318g (0.6 mmol) of the ligand L4Dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain brownish red powdery solid Ni4. The yield was 74.1%. Elemental analysis (C)56H70Br10N4Ni3O2): c,37.24; h,3.91; n,3.10; experimental values (%): c,37.38; h,4.30; and N,3.03.
3) Polymerization:
polymerization of a 7mL stainless Steel glass liner with mechanical agitationThe kettle is dried continuously for 2h at 130 ℃, vacuumized while hot and added with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were poured into the polymerization system3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni were added4The reaction was carried out at 50 ℃ under 15atm of ethylene pressure with stirring for 20min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. Polymerization Activity was 6.27X 106g·mol-1(Ni)·h-1The weight average molecular weight was 12.32 ten thousand, the molecular weight distribution was 3.62, and the molar content of Si monomer was 4.51%. The spheroidal polymer had an average particle size of 0.70mm.
Example 9
Figure BDA0003046376570000221
Complex Ni5Preparation of
Will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.249g (0.6 mmol) of the ligand L in ethanol (10 mL)5In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni5. The yield was 84.3%. Elemental analysis (C)64H66Br6N4Ni3O2): c,48.69; h,4.21; n,3.55; experimental values (%): c,48.54; h,4.47; n,3.21.
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was continuously dried at 130 ℃ for 2h, evacuated while hot and purged with N2Replace qi for 3 times. The polymerization was charged with 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.LL (0.01 mol/L in toluene) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added with 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni5The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 60min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 5.69X 106g·mol-1(Ni)·h-1The weight average molecular weight was 12.34 ten thousand, the molecular weight distribution was 4.27, and the molar content of Si monomer was 4.12%. The average particle size of the spheroidal polymer was 0.79mm.
Example 10
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 450mL of hexane, 5mL (24.1 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 12.3mL of AliBu3(95％)，0.5mL AlMe3(1.0 mol/L in heptane), 6.4mg (12.5. Mu. Mol) of tris (pentafluorophenyl) borane, 11.5mg (12.5. Mu. Mol) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 2.0mg (1.25. Mu. Mol) of complex Ni were added5The reaction was carried out at 20 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. Polymerization Activity was 5.24X 106g·mol-1(Ni)·h-1The weight average molecular weight was 9.07 ten thousand, the molecular weight distribution was 3.84, and the molar content of Si monomer was 4.14%. The average particle diameter mm of the spheroidal polymer in the copolymer was 3.8mm, and the density of the resulting polymer was 0.5517g/cm3。
Example 11
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was dried continuously at 130 ℃ for 2hrs, evacuated while hot and charged with N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added5. The reaction was vigorously stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Acidified with 10% by weight hydrochloric acidNeutralizing with ethanol solution to obtain polymer with polymerization activity of 4.23 × 106g·mol-1(Ni)·h-1Weight average molecular weight was 8.31 ten thousand, molecular weight distribution was 3.24, and molar content of si monomer was 4.26%. The average particle size of the spheroidal polymer was 0.72mm.
Comparative example 3
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L in toluene) were charged into the polymerization system, and 12.5. Mu.L (1.0 mmol/L in toluene) of Ni complex was added5The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 2.24X 106g·mol-1(Ni)·h-1The weight average molecular weight was 5.27 ten thousand, the molecular weight distribution was 4.34, and the molar content of Si monomer was 3.17%. The resulting polymer had no spherical particles.
Example 12
Figure BDA0003046376570000241
The mixture containing 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.389g (0.6 mmol) of ligand L6. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni6. The yield was 74.1%. Elemental analysis (C)52H34Br14N4Ni3O2): c,30.59; h,1.68; n,2.74; experimental values (%): c,30.72; h,1.97; and N,2.48.
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. The polymerization system was charged with 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl)3-butenyl radical) (0.19 mmol), 50. Mu.L of AlMe3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added6The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 4.22X 106g·mol-1(Ni)·h-1Weight average molecular weight was 5.14 ten thousand, molecular weight distribution was 4.24, and si monomer molar content was 4.33%. The average particle size of the spheroidal polymer was 0.68mm.
Example 13
Figure BDA0003046376570000251
Preparation of ligand L7 is described in Organometallics,2013,32,2291-2299.
Complex Ni7(R in the structural formula VIII)1、R3、R4、R6Is methyl, R2、R5、R7-R10、R21-R24Hydrogen, and R' is ethyl, M is nickel, Y is O, X is Br):
the mixture containing 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.264g (0.6 mmol) of ligand L7. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni7. Yield: 78.2 percent. Elemental analysis (C)68H66Br6N4Ni3O2): c,50.21; h,4.09; n,3.44; experimental values (%): c,50.38; h,4.22; and N,3.76.
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. Injection into the polymerization System of 4.0mL of heptane, 40. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.15 mmol), 50. Mu.L of AlMe3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added7The reaction was carried out at 30 ℃ under 15atm of ethylene pressure with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. Polymerization Activity was 2.21X 106g·mol-1(Ni)·h-1The weight average molecular weight was 15.17 ten thousand, the molecular weight distribution was 4.22, and the molar content of Si monomer was 1.08%. The average particle size of the spheroidal polymer was 0.71mm.
Example 14
Figure BDA0003046376570000252
Figure BDA0003046376570000261
Preparation of ligand L8: compound A (1.77g, 5.1mmol) and 2, 6-dimethyl-4-bromo-aniline (2.3g, 11.3mmol), p-toluenesulfonic acid as a catalyst, in 100mL of toluene are refluxed for 1 day, the solvent is removed after filtration, the residue is dissolved with dichloromethane and chromatographed on a petroleum ether/ethyl acetate column to give L8 as a yellow solid in 78% yield.1H NMR(CDCl3，δ，ppm):1.84(s，12H)，1.19ppm(s，18H)，4.70(s，2H)，7.04(8H)，7.12(s，2H)。
Complex Ni8Preparation of (R in structural formula VIII)1、R3、R4、R6Is methyl, R2、R5Is bromine, R7-R10、R22-R24Is hydrogen, R21Is tert-butyl, and R' is ethyl, M is nickel, Y is O, X is Br)
The mixture containing 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise (10 mL) to a dichloromethane solution (10 mL) containing 0.426g (0.6 mmol) of ligand L8. The color of the solution immediately turned deep red and a large amount of precipitate formed. At room temperatureStirring for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain brownish red powdery solid Ni8. The yield was 82.0%. Elemental analysis (C)84H94Br10N4Ni3O2): c,46.56; h,4.37; n,2.59; experimental values (%): c,46.43; h,4.72; and N,2.98.
A7 mL stainless steel glass lined polymerizer equipped with mechanical agitation was dried continuously at 130 ℃ for 2hrs, evacuated while hot and charged with N2Replace qi for 3 times. 4.0mL of heptane was injected, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol) was added, 50. Mu.L of AlMe3 (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, and 12.5. Mu.L (1.0 mmol/L in toluene) of the complex Ni was added8. The reaction was vigorously stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 15 atm. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution, and polymerization activity is 5.33 × 106g·mol-1(Ni)·h-1Weight average molecular weight was 17.64 ten thousand, molecular weight distribution was 4.37, and molar content of si monomer was 1.16%. The average particle size of the spheroidal polymer was 1.24mm.
Comparative example 4
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L in toluene) were charged to the polymerization, and 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni was added8The reaction was carried out at 30 ℃ under 15atm of ethylene pressure with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. Polymerization Activity was 4.21X 105g·mol-1(Ni)·h-1The weight average molecular weight was 10.30 ten thousand, the molecular weight distribution was 4.42, and the molar content of Si monomer was 0.88%. The resulting polymer had no spherical particles.
Example 15
Figure BDA0003046376570000271
1) Ligand L9For the preparation of patent CN 10639264;
2) Complex Ni9Preparation of (R in structural formula VIII)1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22-R24Is hydrogen, R21Is tert-butyl, and R' is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.365g (0.6 mmol) of ligand L9Dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni9. The yield was 82.0%. Elemental analysis (C)92H114Br6N4Ni3O2): c,56.28; h,5.85; n,2.85; experimental values (%): c,56.43; h,6.12; and N,3.08.
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 62. Mu.L of AliBu3 (95%), 50. Mu.L of AlMe3 (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 12.5. Mu.L (1.0 mmol/L in toluene) of the complex Ni complex was added9The reaction was carried out at 30 ℃ under an ethylene pressure of 15atm with stirring for 60min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 1.42X 106g·mol-1(Ni)·h-1The weight average molecular weight was 30.37 ten thousand, the molecular weight distribution was 4.42, and the molar content of Si monomer was 1.13%. The average particle size of the spheroidal polymer was 2.12mm.
Example 16
Figure BDA0003046376570000281
The preparation of ligand L10 is referred to patent CN201510462932.2.
Will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.341g (0.6 mmol) of ligand L10. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni10. The yield was 82.1%. Elemental analysis (C)88H82Br6N4Ni3O2): c,56.13; h,4.39; n,2.98; experimental values (%): c,56.28; h,4.62; and N,3.24.
Continuously drying a 7mL stainless steel glass lined polymerizer equipped with mechanical stirring at 130 ℃ for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 4.0mL of heptane, 100. Mu.L (0.51 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlMe were poured into the polymerization system3(0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of triphenylmethyl tetrakis (pentafluorophenyl) borate, while adding 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni10The reaction was carried out at 30 ℃ under an ethylene pressure of 20atm with stirring for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity was 1.48X 106g·mol-1(Ni)·h-1The weight average molecular weight was 19.27 ten thousand, the molecular weight distribution was 4.20, and the molar content of Si monomer was 1.14%. The average particle size of the spheroidal polymer was 1.98mm.
The catalyst compositions used in the processes of examples 1 to 16 have copolymerization activities of up to 7.27X 106g·mol-1(Ni)·h-1(ii) a Compared with comparative examples 1-4, the copolymerization activity of the catalysts of examples 1-16 is obviously improved, the content of the comonomer is obviously improved, the molecular weight distribution is lower, and the molecular weight of the polymer can be increasedThe regulation and control are carried out in a wider range. Compared with the comparative example, the spherical polymer cannot be obtained, and the spherical particle polymer with higher comonomer Si content can be obtained by adjusting the monomer structure, so that the popularization and application of the technology are facilitated.
While embodiments of the present invention have been described above, the above description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims (23)

1. A method for copolymerizing an olefin-terminal alkenylsilane/siloxane copolymer having a spherical or spheroidal shape, which comprises reacting an olefin and a terminal alkenylsilane/siloxane represented by the formula (1) or a derivative thereof with a catalyst in the presence of an alkane solvent,
Figure FDA0003046376560000011
in the formula (1), L1-L3Independently selected from H, C with or without substituent1-C30Alkyl radical, L4Is C containing substituents1-C30Alkylene, R'1-R’3Is halogen, C with or without substituents1-C10Alkyl, C with or without substituents1-C10An alkoxy group; preferably, L1And L2Are all H, L3Is H, C with or without substituents1-C20Alkyl radical, L4Is C containing substituents1-C20An alkylene group.
2. The copolymerization process according to claim 1, characterized in that:
the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from at least one of metal complexes shown in a formula (I),
Figure FDA0003046376560000012
in the formula (I), R1、R2Independently selected from C containing or not containing substituents1-C30A hydrocarbyl group; r3、R4Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C20Hydrocarbyl radical, adjacent R3And R4Optionally linked to each other to form a ring or ring system; r' is selected from C containing substituent or not containing substituent1-C20A hydrocarbyl group; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C containing substituent or not containing substituent1-C10Hydrocarbyl, substituted or unsubstituted C1-C10A hydrocarbyloxy group;
preferably, M is selected from nickel or palladium; y is selected from O or S; x is selected from halogen, C containing substituent or not containing substituent1-C10Alkyl, substituted or unsubstituted C1-C10An alkoxy group; r' is selected from C containing substituent or not containing substituent1-C20An alkyl group; r3And R4Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20An alkaryl group.
3. The copolymerization method according to claim 2, wherein R is1、R2Independently selected from C containing or not containing substituents1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, preferably, R1、R2Is a group of formula (II):
Figure FDA0003046376560000021
in the formula (II), R1～R5The same or different, each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Alkylaryl radical, R1～R5Optionally joined to each other to form a ring or ring system.
4. The copolymerization process according to claim 2 or 3, characterized in that the metal complex is prepared by: reacting a diimine compound of the formula (A) with MXnAnd R' YH, in the presence of a catalyst,
Figure FDA0003046376560000031
in the formula (A), R1、R2、R3And R4Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same meanings as in formula (I).
5. The copolymerization process of claim 2, wherein the metal complex has a structure according to formula (III):
Figure FDA0003046376560000032
in the formula (III), R5～R8Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30A hydrocarbon group, R5～R8Optionally linked to each other to form a ring or ring system; preferably, R5～R8Independently selected from hydrogen, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10Alkoxy, halogen.
6. The copolymerization process of claim 5, wherein the metal complex has a structure according to formula (IV):
Figure FDA0003046376560000033
in the formula (IV), R1～R11Independently selected from hydrogen, halogen, hydroxyl, C containing substituent or not containing substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
7. The copolymerization process according to claim 5 or 6, characterized in that the metal complex is prepared by: reacting a diimine compound of the formula (B) with MXnAnd R' YH, in the presence of a catalyst,
Figure FDA0003046376560000041
in the formula (B), R5～R8Have the same definition as formula (III); r is1And R2Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same meanings as in formula (I).
8. The copolymerization process of claim 2, wherein the metal complex has a structure according to formula (V):
Figure FDA0003046376560000042
in the formula (V), R5～R7Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30Hydrocarbyl radical, R5～R7Optionally linked to each other to form a ring or ring system; preferably, R5～R7Independently selected from hydrogen, C1-C10Alkyl, halogenated C1-C10Alkyl radical, C1-C10Alkoxy, halogenated C1-C10Alkoxy, halogen.
9. The copolymerization process of claim 8, wherein the metal complex has a structure according to formula (VI):
Figure FDA0003046376560000051
in the formula (VI), R1～R5Independently selected from hydrogen, halogen, C containing substituent or not containing substituent1-C6Alkyl, substituted or unsubstituted C1-C6An alkoxy group; r is5～R10Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6An alkoxy group; m is nickel; y is O; x is selected from halogen; r' is selected from C containing substituent or not containing substituent1-C6An alkyl group.
10. The copolymerization process according to claim 8 or 9, characterized in that the metal complex is prepared by: reacting a diimine compound of the formula (C) with MXnAnd R' YH, in the presence of a catalyst,
Figure FDA0003046376560000052
in the formula (C), R5、R6、R7Has the same definition as formula (V); r is1And R2Have the same definition as formula (I); MXnWherein M and X have the same meanings as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH haveHave the same definitions as in formula (I).
11. The copolymerization process according to claim 2, characterized in that the metal complex has a structure according to formula (VII):
Figure FDA0003046376560000061
in the formula (VII), R21～R24Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Hydrocarbyl, substituted or unsubstituted C1-C20Alkoxy radical, R21～R24Optionally linked to each other to form a ring or ring system; preferably, R21～R24Each independently selected from hydrogen, halogen, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
12. The copolymerization process of claim 11, wherein the metal complex has a structure according to formula (VIII):
Figure FDA0003046376560000062
in the formula (VIII), R1～R10Independently selected from hydrogen, halogen, hydroxyl, C with or without substituent1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C2-C20Alkenyloxy, substituted or unsubstituted C2-C20Alkynyloxy, substituted or unsubstituted C3-C20Cycloalkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C7-C20Aralkyloxy, substituted or unsubstituted C7-C20Alkylaryl, substituted or unsubstituted C7-C20An alkaryloxy group.
13. The copolymerization process according to claim 11 or 12, characterized in that the metal complex is prepared by: reacting a diimine compound of the formula (D) with MXnAnd R' YH, in the presence of a catalyst,
Figure FDA0003046376560000071
in the formula (D), R21～R24Has the same definition as formula (VII); r is1And R2Have the same definition as formula (I); MXnWherein M and X have the same definition as in formula (I), n is the number of X satisfying the valence of M, and n is 1,2 or 3; y and R 'in R' YH have the same meanings as in formula (I).
14. The copolymerization process according to claim 2, characterized in that:
the concentration of the metal complex in a reaction system is 0.00001-100 mmol/L.
15. The copolymerization process according to claim 2, wherein:
the cocatalyst is selected from an organic aluminum compound and/or an organic boron compound, wherein the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate.
16. The copolymerization process of claim 15, wherein:
when the cocatalyst is an organic aluminum compound, the molar ratio of aluminum in the organic aluminum compound to M in the metal complex is (10-10)7): 1, preferably (10 to 100000): 1;
when the cocatalyst comprises an organoboron compound and an organoaluminum compound, the molar ratio of boron in the organoboron compound to M in the metal complex is (0.1 to 1000): 1, the molar ratio of aluminum in the organoaluminum compound to M in the metal complex is (10 to 10)5)：1。
17. The copolymerization process according to claim 1, characterized in that:
the concentration of the terminal alkenyl silane/siloxane or the derivative thereof in a reaction system is 0.01-6000 mmol/L, preferably 0.1-1000 mmol/L.
18. The copolymerization process according to claim 1, characterized in that:
the olefin is an olefin having 2 to 16 carbon atoms, preferably ethylene or an alpha-olefin having 3 to 16 carbon atoms.
19. The copolymerization process according to claim 1, characterized in that:
the reaction temperature is-50 ℃ to 80 ℃, and the reaction time is 10 min to 200min.
20. The copolymerization process according to claim 1, wherein:
the average particle diameter of the spherical or spheroidal copolymer is 0.02 to 50.0mm, preferably 0.2 to 20.0mm.
21. Copolymer obtainable by the copolymerization process according to any one of claims 1 to 20, preferably at least partially spherical or spheroidal copolymer having cavities and pores inside.
22. The copolymer of claim 21, wherein:
the density of the copolymer is 0.3000-0.8500 g/cm3Preferably 0.4000 to 0.7500g/cm3The density is measured by GB/T6343-2009; and/or the presence of a gas in the gas,
the weight average molecular weight of the copolymer is 5,000 to 500,000, preferably 10,000 to 300,000.
23. Use of a copolymer obtainable by a copolymerization process according to any one of claims 1 to 20 as a polyolefin material.
CN202110473860.7A 2021-04-29 2021-04-29 Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer Active CN115260357B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110473860.7A CN115260357B (en) 2021-04-29 2021-04-29 Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110473860.7A CN115260357B (en) 2021-04-29 2021-04-29 Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer

Publications (2)

Publication Number Publication Date
CN115260357A true CN115260357A (en) 2022-11-01
CN115260357B CN115260357B (en) 2023-08-15

Family

ID=83745532

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110473860.7A Active CN115260357B (en) 2021-04-29 2021-04-29 Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer

Country Status (1)

Country Link
CN (1) CN115260357B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050009690A1 (en) * 2003-07-10 2005-01-13 Guangxue Xu Catalyst component for olefin polymerization
DE102005024815A1 (en) * 2005-05-27 2006-11-30 Degussa Ag Preparation of composition containing functionalized polyhedral silicon-oxygen oligomer cluster, useful for synthesizing catalyst, ceramic masses and polymers, comprises conversion of two different silanes under base catalyst
CN101125897A (en) * 2006-08-18 2008-02-20 中国石油化工股份有限公司 Catalyst used for olefin polymerization reaction
US20140343237A1 (en) * 2011-09-20 2014-11-20 Toho Titanium Co., Ltd. Solid catalyst component for polymerization of olefin, catalyst for polymerization of olefin, and method for producing olefin polymer
CN105152970A (en) * 2015-06-25 2015-12-16 中国科学技术大学 Diimine palladium catalyst with great steric hindrance, and ligand, preparation method and application thereof
US20190077888A1 (en) * 2016-03-16 2019-03-14 Jxtg Nippon Oil & Energy Corporation Method for producing oligomer and catalyst
US20200140577A1 (en) * 2017-05-10 2020-05-07 Toho Titanium Co., Ltd. CATALYST FOR POLYMERIZATION OF AN OLEFIN, METHOD FOR PRODUCING POLYMER OF OLEFIN AND PROPYLENE-alpha-OLEFIN COPOLYMER
CN111116808A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-olefin alcohol copolymer
CN111116806A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-unsaturated carboxylic acid copolymer
CN111116807A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-olefin alcohol copolymer

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050009690A1 (en) * 2003-07-10 2005-01-13 Guangxue Xu Catalyst component for olefin polymerization
DE102005024815A1 (en) * 2005-05-27 2006-11-30 Degussa Ag Preparation of composition containing functionalized polyhedral silicon-oxygen oligomer cluster, useful for synthesizing catalyst, ceramic masses and polymers, comprises conversion of two different silanes under base catalyst
CN101125897A (en) * 2006-08-18 2008-02-20 中国石油化工股份有限公司 Catalyst used for olefin polymerization reaction
US20140343237A1 (en) * 2011-09-20 2014-11-20 Toho Titanium Co., Ltd. Solid catalyst component for polymerization of olefin, catalyst for polymerization of olefin, and method for producing olefin polymer
CN105152970A (en) * 2015-06-25 2015-12-16 中国科学技术大学 Diimine palladium catalyst with great steric hindrance, and ligand, preparation method and application thereof
US20190077888A1 (en) * 2016-03-16 2019-03-14 Jxtg Nippon Oil & Energy Corporation Method for producing oligomer and catalyst
US20200140577A1 (en) * 2017-05-10 2020-05-07 Toho Titanium Co., Ltd. CATALYST FOR POLYMERIZATION OF AN OLEFIN, METHOD FOR PRODUCING POLYMER OF OLEFIN AND PROPYLENE-alpha-OLEFIN COPOLYMER
CN111116808A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-olefin alcohol copolymer
CN111116806A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-unsaturated carboxylic acid copolymer
CN111116807A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Preparation method of olefin-olefin alcohol copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡友良;: "烯烃配位聚合催化剂和聚合反应", 石油化工, no. 06, pages 55 - 59 *

Also Published As

Publication number Publication date
CN115260357B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
CN111116802A (en) Preparation method of olefin-unsaturated carboxylic acid copolymer
CN111116801B (en) Preparation method of olefin-unsaturated carboxylic acid copolymer
CN112745419B (en) Process for producing olefin-unsaturated carboxylic acid copolymer and olefin-unsaturated carboxylic acid copolymer
CN112745359B (en) Diimine metal complex and preparation method and application thereof
CN111116809B (en) Olefin-olefin alcohol copolymer and preparation method thereof
CN115260357B (en) Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer
CN112745361B (en) Diimine complex and preparation method and application thereof
CN112745362B (en) Diimine metal complex and preparation method and application thereof
CN112745423B (en) Preparation method of olefin-unsaturated carboxylic acid copolymer, olefin-unsaturated carboxylic acid copolymer and application thereof
CN112745429B (en) Process for producing olefin-unsaturated carboxylic acid copolymer
CN115260360B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane, copolymer and application thereof
CN111116810B (en) Preparation method of olefin-olefin alcohol copolymer
CN108359038B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN115260368B (en) Polymerization method of ethylene-internal olefin-diene copolymer and copolymer obtained by polymerization method
CN113754817B (en) Method for preparing olefin copolymer with polar group and product thereof
CN113754815B (en) Process for preparing olefin-olefin alcohol copolymers
CN113754818B (en) Method for producing olefin-olefin alcohol copolymer and olefin-olefin alcohol copolymer
CN112745420B (en) Method for preparing olefin-unsaturated carboxylic acid copolymer
CN112745425B (en) Process for preparing olefin-olefin alcohol copolymers
CN115260364B (en) Application of diimine metal complex in catalyzing olefin polymerization
CN112745422B (en) Method for preparing olefin-olefin alcohol copolymer
CN113754819B (en) Method for preparing olefin copolymer with carboxyl
CN115260363B (en) Application of metal complex in catalyzing olefin polymerization
CN115246900B (en) Polymer preparation method and polymer
CN112745427B (en) Method for preparing olefin-olefin alcohol copolymer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant