CN108456272B - Catalyst composition for olefin polymerization, application thereof and method for polymerizing conjugated diene monomer - Google Patents
Catalyst composition for olefin polymerization, application thereof and method for polymerizing conjugated diene monomer Download PDFInfo
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- CN108456272B CN108456272B CN201710089717.1A CN201710089717A CN108456272B CN 108456272 B CN108456272 B CN 108456272B CN 201710089717 A CN201710089717 A CN 201710089717A CN 108456272 B CN108456272 B CN 108456272B
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- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Abstract
The invention relates to the field of catalysts for polymerization, and discloses a catalyst composition for olefin polymerization, application thereof and a method for polymerizing conjugated diene monomers, wherein the catalyst composition for olefin polymerization contains a main catalyst and a cocatalyst, the main catalyst is a bis-Schiff base rare earth complex, the complex has a structure shown in a formula (1), and the cocatalyst comprises an alkylating agent and/or an organic boron compound; the method for polymerizing conjugated diene monomers comprises: a starting material comprising conjugated diene monomer is contacted with a catalyst composition to effect polymerization. The catalyst composition for olefin polymerization provided by the invention can catalyze homopolymerization of conjugated diene monomers and copolymerization of the conjugated diene monomers and polar monomers. The catalyst composition for olefin polymerization has the advantages of high conversion rate and high cis-structure content when used for catalyzing homopolymerization and copolymerization of conjugated diene monomers.
Description
Technical Field
The invention relates to the field of catalysts for polymerization, in particular to a catalyst composition for olefin polymerization, application of the catalyst composition for olefin polymerization in catalyzing polymerization of conjugated diene monomers and a method for polymerizing the conjugated diene monomers.
Background
Conjugated dienes such as butadiene and isoprene can be used to synthesize stereoregular polymers by coordination polymerization to produce important synthetic rubber varieties such as cis-1, 4-polybutadiene and cis-1, 4-polyisoprene.
Various organic complexes of transition metals, post-transition metals, and rare earth metals are useful as catalysts for the polymerization of conjugated dienes. However, the copolymerization of the conjugated diene with other olefins, polar monomers and the like is not easy to realize, and particularly, the polar monomers are easy to destroy catalytic active centers, so that the catalyst is inactivated. However, the introduction of polar groups into conjugated diene homopolymers can improve the properties of the materials or impart new properties to the materials.
An organometallic complex with a new structure is synthesized, and the catalytic characteristics of the organometallic complex in the fields of conjugated olefin homopolymerization and copolymerization are researched.
CN101693754A provides a tridentate carbazolyl chelated rare earth complex, and the tridentate carbazolyl chelated rare earth complex is used for copolymerization of conjugated diene and polar monomer. The catalyst consists of rare earth complex of tridentate carbazolyl chelate, organic boron salt and alkylating reagent, and the molar ratio of each component is 1: 1: 0 to 1: 1: 100, can be used for the copolymerization of conjugated dienes and polar monomers to obtain block copolymers.
CN102321200A provides a catalytic application of fluorene rare earth metal catalyst in olefin coordination polymerization, carbon dioxide and epoxide polymerization or alkyne polymerization.
The rare earth metals mainly include 17 elements in total, such as scandium, yttrium, and lanthanoid metals, and are arranged in group IIIB of the periodic table. The rare earth metal organic complex has properties different from those of the transition metal element compound. Schiff base (schiffbase) mainly refers to a class of organic compounds containing imine or azomethine characteristic groups (-RC ═ N-), and is generally formed by condensation of amine and active carbonyl. Schiff base ligands are characterized by greater flexibility in the synthesis process. Various amino compounds are selected to react with different aldehydes or ketones to obtain Schiff base ligands with variable structures and different properties, and the Schiff base ligands are important organic ligands. The complex prepared by the reaction of the Schiff base ligand and the metal has important application in a plurality of fields such as photochromism, catalysis, medicine and the like.
Disclosure of Invention
The invention aims to provide a rare earth catalytic system for homopolymerization and/or copolymerization of conjugated diene.
The catalyst system provided by the invention is a rare earth catalyst system for homopolymerization and copolymerization of conjugated diene monomers, and the scheme of the invention is provided based on that a catalyst system formed by a novel symmetric bis-Schiff base rare earth complex and an alkylating agent and/or organoboron can catalyze homopolymerization of conjugated diene monomers and copolymerization of the conjugated diene monomers and polar monomers.
In order to achieve the above object, the present invention provides, in a first aspect, a catalyst composition for olefin polymerization, comprising a main catalyst and a cocatalyst, wherein the main catalyst is a bis-schiff base rare earth complex having a structure represented by formula (1), and the cocatalyst comprises an alkylating agent and/or an organoboron compound,
wherein R is1And R2Each independently selected from C1-6Alkyl and C1-6A group of at least one of alkoxy groups of (a);
ln is a rare earth metal element of group IIIB.
In a second aspect, the present invention provides the use of the aforementioned catalyst composition for olefin polymerization for catalyzing the polymerization of conjugated diene monomer.
In a third aspect, the present invention provides a process for polymerizing conjugated diene monomer, the process comprising: in the presence of a solvent, a raw material including a conjugated diene monomer is contacted with a catalyst composition for olefin polymerization described above to carry out a polymerization reaction.
The catalyst composition for olefin polymerization provided by the invention can catalyze homopolymerization of conjugated diene monomers and copolymerization of the conjugated diene monomers and polar monomers.
The catalyst composition for olefin polymerization has the advantages of high conversion rate and high cis-structure content when used for catalyzing homopolymerization and copolymerization of conjugated diene monomers.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
First aspectThe invention provides a catalyst composition for olefin polymerization, which contains a main catalyst and an auxiliary catalyst, wherein the main catalyst is a bis-Schiff base rare earth complex which has a structure shown in a formula (1), the auxiliary catalyst comprises an alkylating reagent and/or an organic boron compound,
wherein R is1And R2Each independently selected from C1-6Alkyl and C1-6A group of at least one of alkoxy groups of (a);
ln is a rare earth metal element of group IIIB. The rare earth metal elements of group IIIB include yttrium element, scandium element, lanthanoid element, and actinide element.
Said C is1-6Alkyl of (a) represents: alkyl groups having a total number of carbon atoms of 1 to 6 which are unsubstituted or substituted by halogen.
Said C is1-6The alkoxy group of (a) represents: alkoxy groups having a total number of carbon atoms of 1 to 6 which are unsubstituted or substituted by halogen.
Preferably, in formula (1), R1And R2Each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, primary butoxy, sec-butoxy and tert-butoxy; r1And R2Each independently selected from at least one member of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, methoxy, ethoxy, n-propoxy, isopropoxy, and primary butoxy; more preferably, R1And R2Each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, and primary butyl.
Preferably, Ln is praseodymium element, neodymium element, samarium element, yttrium element, gadolinium element or scandium element; more preferably, Ln is neodymium element, yttrium element, or gadolinium element.
According to a first preferred embodiment, in formula (1), R1And R2Each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, primary butoxy, sec-butoxy and tert-butoxy; ln is praseodymium element, neodymium element and samarium elementElemental, yttrium, gadolinium or scandium.
According to a second preferred embodiment, in formula (1), R1And R2Each independently selected from at least one member of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, methoxy, ethoxy, n-propoxy, isopropoxy, and primary butoxy; ln is neodymium element, yttrium element or gadolinium element.
According to a third preferred embodiment, in formula (1), R1And R2Groups each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, and primary butyl; ln is neodymium element, yttrium element or gadolinium element. The inventors of the present invention have found that the catalyst composition for olefin polymerization provided by the preferred embodiment can significantly improve the monomer conversion rate and increase the cis content of the product when catalyzing the polymerization of conjugated diene monomer.
The method for preparing the bis-schiff base rare earth complex is not particularly limited, and those skilled in the art can synthesize the bis-schiff base rare earth complex by various methods conventional in the art. Particularly preferably, the invention provides the following method for preparing the bis-schiff base rare earth complex.
The method for preparing the bis-schiff base rare earth complex comprises the following steps:
a bis-Schiff base compound shown as a formula (2) and LnCl3(THF)3The reaction is carried out, and the reaction solution is mixed,
wherein, R is1、R2Ln is as defined above in the invention; and X in the formula (2) is halogen.
Preferably, the bis-schiff base compound represented by the formula (2) is reacted with LnCl3(THF)3The conditions under which the reaction is carried out include: the temperature is 100 ℃ below zero to 50 ℃ above zero, and the time is 5-48 h.
Preferably, in the present invention, the bis-schiff base compound represented by formula (2) is reacted with LnCl3(THF)3The step of performing the reaction comprises: firstly, bis-Schiff base compound shown as formula (2) reacts with butyl lithium at the temperature of minus 100 ℃ to minus 30 ℃ to obtain t1For a while, then the product obtained is reacted with LnCl3(THF)3At-50 ℃ to contact t2Time, wherein t1+t2Namely, the bis-Schiff base compound represented by the formula (2) and LnCl are mixed according to the invention3(THF)3Reaction time in the conditions under which the reaction is carried out. Preferably, the molar ratio of the bis-schiff base compound shown in the formula (2) to the butyl lithium is 1: (1-1.8).
Preferably, the bis-Schiff base compound represented by the formula (2) is reacted with LnCl3(THF)3The molar ratio of the used amount of the compound is 1: (1-2).
Preferably, the bis-schiff base compound represented by the formula (2) is prepared by the following steps:
1) carrying out a first reaction on a compound with a structure shown in a formula (4) and a compound with a structure shown in a formula (5) under an acidic condition to obtain a compound with a structure shown in a formula (6);
2) carrying out a second reaction on the compound with the structure shown in the formula (6) in the presence of protective gas and a self-coupling catalyst;
wherein R in the formula (2), the formula (5) and the formula (6)1And R2The same applies to the formula (2), and X in the formula (4) and the formula (6) is the same.
Preferably, in step 1), the first reaction is carried out in the presence of at least one solvent selected from the group consisting of methanol, ethanol and isopropanol; more preferably, the first reaction is carried out in the presence of a methanol solvent.
Preferably, in step 1), the conditions of the first reaction include: the temperature is 5-40 deg.C, the time is 4-24h, and the pH value is 5-6.
In step 1), the acidic condition may be formed by adding an acidic substance selected from at least one of formic acid, acetic acid and propionic acid to the system; preferably, the acidic substance is acetic acid. The amount of the acidic substance added is such that the first reaction is carried out at a pH of 5 to 6.
In step 2), the protective gas is preferably nitrogen and/or argon.
Preferably, in step 2), the second reaction is carried out in the presence of at least one solvent selected from the group consisting of tetrahydrofuran, chlorobenzene, chloroform, tetrahydronaphthalene, methyl chloride and dioxane.
In step 1) and step 2) of the present invention, the molar ratio of the amount of the compound having the structure represented by formula (4), the compound having the structure represented by formula (5), and the compound having the structure represented by formula (6) is not particularly limited, and those skilled in the art can determine the molar ratio of the amount of the reactants according to the type of the reaction and the reaction equation of the relevant reaction, unless otherwise specified.
Preferably, in step 2), the conditions of the second reaction include: the temperature is 5-40 deg.C, and the time is 6-20 h.
Preferably, in the step 2), the self-coupling catalyst is at least one of compounds represented by formula (7), and in the formula (7), M is an alkali metal element;
the alkali metal elements comprise lithium element, sodium element, potassium element, rubidium element and cesium element.
More preferably, in step 2), the self-coupling catalyst is at least one of compounds having a structure represented by formula (7); and in the formula (7), M is a lithium element, a sodium element or a potassium element.
Particularly preferably, in the step 2), the self-coupling catalyst is a compound having a structure represented by the formula (7); and in the formula (7), the M is a lithium element.
The amount of the self-coupling catalyst used in the present invention is not particularly limited, and can be selected by those skilled in the art according to the amount of the catalyst used conventionally in the art. Some amounts of the self-coupling catalyst are exemplified in the examples of the present invention and those skilled in the art should not be construed as limiting the invention.
Preferably, the compound with the structure shown in the formula (4) is prepared by the following steps:
a. in the presence of an organic solvent, carrying out a first reflux reaction on a compound with a structure shown in a formula (3), N-bromosuccinimide and azobisisobutyronitrile, and sequentially filtering and removing the solvent from a solid-liquid mixture obtained after the reflux reaction;
b. carrying out a second reflux reaction on the product subjected to the solvent removal treatment in the step a) and a carboxylic acid solution;
wherein X in formula (3) corresponds to the same X in formula (2).
The compound having the structure represented by formula (4) obtained after the second reflux reaction is a crude product containing impurities, and a person skilled in the art may perform a post-treatment operation to purify the compound having the structure represented by formula (4) by using a post-treatment method conventionally used in the art, which is not particularly limited in the present invention. For example, the invention can sequentially carry out solvent removal, extraction, separation and purification on the material obtained after the second reflux reaction. The separation and purification method can be performed by, for example, column chromatography.
The solvent removal treatment of the present invention can be carried out, for example, by atmospheric distillation or reduced pressure rotary evaporation.
Preferably, in step a), the time of the first reflux reaction is 8-48 h.
Preferably, in step a), the organic solvent is at least one selected from the group consisting of carbon tetrachloride, toluene, xylene, and 1, 2-dichloropropane. More preferably, in step a), the organic solvent is carbon tetrachloride.
Preferably, in step a), the compound having the structure represented by formula (3), N-bromosuccinimide and azobisisobutyronitrile are used in a molar ratio of 1: (2-4): (0.008-0.12).
Preferably, in step b), the time of the second reflux reaction is 6-24 h; more preferably, the time of the second reflux reaction is 8 to 20 hours.
Preferably, in step b), the carboxylic acid is selected from at least one of formic acid, acetic acid and propionic acid. More preferably, the carboxylic acid is formic acid, i.e., the carboxylic acid solution may be a formic acid solution. The concentration of the carboxylic acid solution may be 35 to 99 wt%. The amount of the carboxylic acid used in the process of the present invention is not particularly limited, and those skilled in the art can select the amount according to the conventional amount in the art, and in order to clearly illustrate the optional amount of the carboxylic acid of the present invention, some amounts of the carboxylic acid are exemplified in the examples of the present invention, and those skilled in the art should not be construed as limiting the present invention.
In the above method for preparing bis-schiff base rare earth complexes of the present invention, the intermediate products or target products obtained in each step can be purified by various methods conventional in the art, and the purification method of the present invention is not particularly limited, and in the examples of the present invention, the purification is performed by a column chromatography method. Preferably, the eluent used in column chromatography is petroleum ether and CH2Cl2The mixed reagent of (1).
According to a preferred embodiment, the method for preparing the bis-schiff base rare earth complex having the structure represented by formula (1) comprises:
a) in the presence of an organic solvent, carrying out a first reflux reaction on a compound with a structure shown in a formula (3), N-bromosuccinimide and azobisisobutyronitrile, and sequentially filtering and removing the solvent from a solid-liquid mixture obtained after the reflux reaction;
b) carrying out a second reflux reaction on the product subjected to the solvent removal treatment in the step a) and a carboxylic acid solution to obtain a compound with a structure shown in a formula (3);
c) carrying out a first reaction on a compound with a structure shown in a formula (4) and a compound with a structure shown in a formula (5) under an acidic condition to obtain a compound with a structure shown in a formula (6);
d) carrying out a second reaction on the compound with the structure shown in the formula (6) in the presence of protective gas and a self-coupling catalyst to obtain a compound with the structure shown in the formula (2);
e) a bis-Schiff base compound shown as a formula (2) and LnCl3(THF)3Carrying out reaction;
wherein R is1、R2And X is as defined above in the invention.
Preferably, the alkylating agent is selected from at least one of an aluminum alkyl, an aluminum alkyl hydride, and an aluminoxane.
Preferably, the alkyl aluminum is selected from at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, triphenyl aluminum, tribenzyl aluminum, and diethyl benzyl aluminum.
Preferably, the aluminum alkyl hydride is selected from at least one of diethylaluminum hydride, dibutylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride and dibenzylaluminum hydride.
Preferably, the aluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane.
The "organoboron compound" of the present invention means a hydrocarbyl-substituted borane or borate. Preferably, the organoboron compound is selected from tris (pentafluorophenyl) boron (B (C)6F5)3) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate ([ HNMe)2Ph][B(C6F5)4]) And triphenylcarbenium tetrakis (pentafluorophenyl) borate ([ Ph)3C][B(C6F5)4]) At least one of (1). Particularly preferably, the organoboron compound is [ Ph3C][B(C6F5)4]。
The present invention provides several preferred embodiments as follows with respect to the composition of the catalytic system of the present invention.
Embodiment mode 1: the cocatalyst is an alkylating agent or an organic boron compound; the molar ratio of the content of the main catalyst in terms of rare earth metal elements to the content of the cocatalyst is 1: (0.1-100).
Embodiment mode 2: the cocatalyst is an alkylating agent and an organic boron compound; the molar ratio of the content of the main catalyst calculated by rare earth metal elements to the content of the alkylating agent and the organoboron compound is 1: (1-100): (0.1-3).
Embodiment mode 3: the cocatalyst is aluminum alkyl, and the molar ratio of the content of the main catalyst in terms of rare earth metal elements to the content of the cocatalyst is 1: (5-100).
Embodiment 4: the promoter is an organic boron compound, and the molar ratio of the content of the main catalyst calculated by rare earth metal elements to the content of the promoter is 1: (0.5-3).
Embodiment 5: the cocatalyst is an alkyl aluminum and an organic boron compound, and the molar ratio of the content of the main catalyst in terms of rare earth metal elements to the content of the alkyl aluminum and the organic boron compound is 1: (1-100): (0.1-3).
Second aspect of the inventionThe invention provides application of the catalyst composition for olefin polymerization in catalyzing polymerization of conjugated diene monomers.
Third aspect of the inventionThe present invention provides a method for polymerizing conjugated diene monomer, comprising: in the presence of a solvent, a raw material including a conjugated diene monomer is contacted with a catalyst composition for olefin polymerization described above to carry out a polymerization reaction.
The catalyst composition for olefin polymerization according to the third aspect of the present invention is the catalyst composition for olefin polymerization according to the first aspect of the present invention, and details of the composition of the catalyst composition for olefin polymerization are not repeated in the third aspect of the present invention.
Preferably, the polymerization conditions include: the temperature is from minus 30 ℃ to plus 100 ℃, and the time is from 10min to 24 h; more preferably, the polymerization conditions include: the temperature is between 25 ℃ below zero and 80 ℃ above zero, and the time is between 30min and 12 h.
Preferably, in the polymerization reaction, the molar ratio of the amount of the catalyst composition for olefin polymerization calculated on the basis of the rare earth metal element to the amount of the conjugated diene monomer is 1: (200-5000).
Preferably, the solvent is selected from C5-10Alkane, C5-10At least one of cycloalkane of (a), benzene, toluene, xylene, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, dichlorobenzene, and tetrahydronaphthalene.
In the present invention, said C5-10Alkane and C5-10The cycloalkane of (a) may include, for example, at least one of pentane, hexane, cyclohexane, heptane and octane.
Preferably, the polymerization reaction is at least one of a copolymerization reaction of the conjugated diene monomer with the polar monomer and a homopolymerization reaction of the conjugated diene monomer.
The "polar monomer" of the present invention means: a monomer having a polar functional group such as an ester group, an epoxy group, an ether group and the like, and an unsaturated bond.
Preferably, the conjugated diene monomer is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; more preferably, the conjugated diene monomer is butadiene and/or isoprene.
Preferably, the polar monomer is at least one of caprolactone, butyrolactone, valerolactone, lactide, propylene oxide and cyclohexene oxide.
Preferably, in the copolymerization of the conjugated diene monomer and the polar monomer, the molar ratio of the conjugated diene monomer to the polar monomer is 1: (0.01-1).
In the present invention, the catalyst composition for olefin polymerization may be prepared in advance or the components of the catalyst composition for olefin polymerization may be added directly to the polymerization reaction system.
The method of preparing the catalyst composition for olefin polymerization in advance may include: mixing a main catalyst and a cocatalyst which form the catalyst composition for olefin polymerization in the presence of a solvent for later use; or mixing the main catalyst and the cocatalyst which form the catalyst composition for olefin polymerization and aging for later use.
In the polymerization reaction of the present invention, it may be further comprised that an ethanol solution such as hydrochloric acid is added to the polymerization reaction system as a terminator to terminate the polymerization reaction after the polymerization reaction is terminated.
The present invention will be described in detail below by way of examples. In the following preparations and examples, various materials used were commercially available without specific description. And each raw material in the preparation examples and the examples is analytically pure.
The following monomer conversion rate is measured by a gravimetric method, and the calculation formula is as follows: conversion (%) - ((weight of sample after drying (g) — added amount of catalyst (g)) × 100/(weight of sample before drying (g) × concentration of monomer (% by weight))); the cis-1, 4-structure content is determined by infrared and nuclear magnetic methods.
Preparation example 1
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH3；R2Is CH3。
1.2, 6-Dimethylbromobenzene (10mmol), NBS (30mmol) and AIBN (0.2mmol) were dissolved in 50mL of CCl4And refluxing for 10h, cooling, filtering, and spin-drying the filtrate. 88 wt.% formic acid (35mL) was added to the solution and refluxing continued for 12 h. Then, the solvent was distilled off under reduced pressure, and the mixture was distilled off using a solvent in a volume ratio of 1: 1.5 CH2Cl2/H2Extracting with O, separating organic phase, and extracting with anhydrous Na2SO4Drying and then adding petroleum ether: CH (CH)2Cl25: 1 (volume ratio) to obtain an intermediate product 2-bromo-3-benzyl bromide-benzaldehyde;
2. dissolving 2-bromo-3-benzyl bromide-benzaldehyde (3.6mmol) in 30mL of methanol, adding 2, 6-dimethyl-aniline (3.6mmol) and acetic acid to make the pH value of the solution 5, reacting at 25 ℃ for 8h, filtering, and collecting precipitate to obtain Schiff base;
3. schiff base (2.62mmol) was added to a 100mL round bottom flask, and 10mL was added under nitrogenTHF and lithium diphenylphosphide (0.05mmol) were reacted at 25 ℃ for 12h, and then the solvent was removed by stirring with a solvent in a volume ratio of 1: 1.5 CH2Cl2/H2Extracting with O, separating organic phase, and extracting with anhydrous Na2SO4Drying, followed by treatment with petroleum ether: CH (CH)2Cl22: 1 (volume ratio) column chromatography separation to obtain the bis-schiff base compound with the yield of 77 percent.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,J＝6.0Hz,2H),7.37(t,J＝6.8Hz,4H),7.10(d,J＝5.2Hz,4H),6.99(t,J＝4.8Hz,2H),3.18(s,4H),2.20(s,12H)。
elemental analysis: c32H30N2Br2Calculated values: c, 63.08; h, 5.02; and N, 4.65. Measured value: c, 63.13; h, 5.05; n, 4.62.
(2) Preparing a compound with a structure shown in a formula (1), wherein Ln is Nd
The obtained bis-Schiff base compound (1mmol) was dissolved in THF to give a 0.04M solution, a solution of butyllithium (1.2mmol) in hexane (30mL) was added, the reaction was stirred at-78 deg.C for 1 hour, then the temperature was raised to-45 deg.C, and NdCl was slowly added3(THF)3(1.8mmol) and then heated to 30 ℃ for reaction for 10 hours to obtain the bis-Schiff base rare earth complex P1.
Preparation example 2
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH3CH2；R2Is CH3CH2。
The compound represented by the formula (2) was prepared in a similar manner to preparation example 1 to give a bis-schiff base compound in 75% yield.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.10(d,4H),7.18(t,2H),2.61(m,8H),1.36(s,12H)。
elemental analysis: c36H38N2Br2Calculated values: c, 65.67; h,5.78(ii) a And N, 4.26. Measured value: c, 65.69; h, 5.78; and N, 4.23.
(2) A compound having a structure represented by formula (1) wherein Ln is Nd was prepared in a similar manner to preparation example 1.
The obtained bis-Schiff base compound (1mmol) was dissolved in THF to give a 0.04M solution, a solution of butyllithium (1.05mmol) in hexane (20mL) was added, the reaction was stirred at-78 deg.C for 1 hour, then the temperature was raised to-40 deg.C, and NdCl was slowly added3(THF)3(1.5mmol) and then heated to 25 ℃ for reaction for 12 hours to obtain the bis-Schiff base rare earth complex P2.
Preparation example 3
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH (CH)3)2；R2Is CH (CH)3)2。
The compound having the structure represented by formula (2) was prepared in a similar manner to preparation example 1 to give a bis-schiff base compound in 73% yield.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.08～7.12(m,6H),3.02～3.08(m,4H),1.23(d,12H)。
elemental analysis: c40H46N2Br2Calculated values: c, 67.24; h, 6.44; n, 3.92. Measured value: c, 67.23; h, 6.44; and N, 3.91.
(2) A compound having a structure represented by formula (1) wherein Ln is Nd was prepared in a similar manner to preparation example 2.
Obtaining the bis-Schiff base rare earth complex P3.
Preparation example 4
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH3；R2Is CH3CH2。
The compound represented by the formula (2) was prepared in a similar manner to preparation example 1 to give a bis-schiff base compound in a yield of 69%.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.1(d,4H),7.08(t,2H),2.52(m,4H),2.21(d,6H),1.26(t,6H)。
elemental analysis: c34H34N2Br2Calculated values: c, 64.78; h, 5.40; n, 4.44. Measured value: c, 64.80; h, 5.41; and N, 4.40.
(2) Preparing a compound with a structure shown in a formula (1), wherein Ln is Y.
The obtained bis-Schiff base compound (1mmol) was dissolved in THF to give a 0.05M solution, a solution of butyllithium (1.4mmol) in hexane (50mL) was added, the reaction was stirred at-78 deg.C for 1 hour, then the temperature was raised to-30 deg.C, and YCl was slowly added3(THF)3(1.8mmol) and then heated to 30 ℃ for reaction for 12 hours to obtain the bis-Schiff base rare earth complex P4.
Preparation example 5
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH3；R2Is CH (CH)3)2。
The compound having the structure represented by formula (1) was prepared in a similar manner to preparation example 1 to give a bis-schiff base compound in 65% yield.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.1(d,4H),7.06(t,2H),3.22(m,2H),2.23(s,6H),1.26(t,12H)。
elemental analysis: c36H38N2Br2Calculated values: c, 65.67; h, 5.78; and N, 4.26. Measured value: c, 65.68; h, 5.79; and N, 4.23.
(2) A compound having a structure represented by formula (1) wherein Ln is Y was prepared in a similar manner to preparation example 4.
Obtaining the bis-Schiff base rare earth complex P5.
Preparation example 6
(1) Preparing a compound with a structure shown in a formula (2), wherein X is Br; r1Is CH3CH2；R2Is CH (CH)3)2。
The compound represented by the formula (2) was prepared in a similar manner to preparation example 1 to give a bis-schiff base compound in a yield of 64%.
The characterization data of the obtained bis-schiff base compound are as follows:
1H NMR(CDCl3,400MHz,δ,ppm):8.74(s,2H),8.14(d,2H),7.37(t,4H),7.1(d,4H),7.06(t,2H),3.22(m,2H),2.45(m,4H),1.26(d,12H),1.21(t,6H)。
elemental analysis: c38H42N2Br2Calculated values: c, 66.49; h, 6.12; and N, 4.08. Measured value: c, 66.5; h, 6.08; and N, 4.09.
(2) A compound having a structure represented by formula (1) wherein Ln is Y was prepared in a similar manner to preparation example 4.
Obtaining the bis-Schiff base rare earth complex P6.
Example 1
To a 500mL polymerization flask were added 0.062mmol of the rare earth complex P1 and 10mL of xylene, followed by 1.86mmol of triisobutylaluminum, and mixed at 25 ℃ for 10 min. 300ml of an isoprene hexane solution (isoprene monomer: 58mmol) was added to the polymerization flask, and the mixture was reacted at 25 ℃ for 130min with stirring. Then 30mmol of butyrolactone monomer is added, the temperature is raised to 70 ℃, and the reaction is continued for 6 h. The reaction was then quenched by the addition of 1mL of a 10% by volume solution of concentrated HCl in ethanol, the reaction solution was treated with ethanol, and the white polymer that had settled out was dried in a vacuum oven at 40 ℃ for 48 h. The total conversion was found to be 76%, the content of butyrolactone segments in the copolymer was 23 mol%, and the content of cis-1, 4-structure of polyisoprene segments was 97.2 wt%.
Example 2
To a 500mL polymerization flask were added 0.062mmol of rare earth complex P2 and 300mL of chlorobenzene, followed by 1.24mmol of triisobutylaluminum and then 0.042mmol of [ PhMe2NH][B(C6F5)4]. Then 50mmol of isoprene monomer was added to the polymerization flask and reacted at 25 ℃ for 150min with stirring. Then, 1mL of a 10 vol% ethanol solution of concentrated hydrochloric acid was added to terminate the reaction, the reaction solution was treated with ethanol, and white precipitate was obtainedThe colored polymer was placed in a vacuum oven and dried at 40 ℃ for 48h to give a white homopolymer. It was found that the monomer conversion was 89.2% and the polyisoprene cis-1, 4-structure content was 97.2% by weight.
Example 3
To a 500mL polymerization flask was added 0.062mmol of rare earth complex P3 and 20mL of toluene, followed by 0.068mmol of [ Ph ]3C][B(C6F5)4]. Then 50mmol of isoprene monomer was added to the polymerization flask and reacted at 25 ℃ for 120min with stirring. Then, 1mL of a 10 vol% ethanol solution of concentrated hydrochloric acid was added to terminate the reaction, the reaction solution was treated with ethanol, and the precipitated white polymer was dried in a vacuum oven at 40 ℃ for 48 hours to obtain a white homopolymer. It was found that the monomer conversion was 90.2% and the polyisoprene cis-1, 4-structure content was 97.3% by weight.
Example 4
To a 500mL polymerization flask were added 0.062mmol of the rare earth complex P4 and 300mL of toluene, followed by 0.62mmol of triisobutylaluminum, mixed at 25 ℃ for 10min, followed by 0.062mmol of [ Ph ]3C][B(C6F5)4]. Then 50mmol of isoprene monomer was added to the polymerization flask and reacted at 25 ℃ for 100min with stirring. Then 20mmol of lactide monomer is added, the temperature is raised to 60 ℃, and the reaction is continued for 4 hours. Then, 1mL of a 10 vol% ethanol solution of concentrated hydrochloric acid was added to terminate the reaction, the reaction solution was treated with ethanol, and the precipitated white polymer was dried in a vacuum oven at 40 ℃ for 48 hours to obtain a white copolymer. The total conversion was found to be 75.6%, the lactide segment content in the copolymer was 16 mol%, and the cis 1, 4-structure content of the polyisoprene segment was 97.1 wt%.
Example 5
To a 500mL polymerization flask was added 0.062mmol of rare earth complex P1 and 10mL of xylene, followed by 3.10mmol of methylaluminoxane, and mixed at 25 ℃ for 10 min. 300mL of an isoprene hexane solution (58 mmol of isoprene monomer) was added to the polymerization flask, and the mixture was reacted at 40 ℃ for 120min with stirring. Then 30mmol of butyrolactone monomer is added, the temperature is raised to 70 ℃, and the reaction is continued for 6 h. The reaction was then quenched by the addition of 1mL of a 10% by volume solution of concentrated HCl in ethanol, the reaction solution was treated with ethanol, and the white polymer that had settled out was dried in a vacuum oven at 40 ℃ for 48 h. The total conversion was found to be 70%, the content of butyrolactone segments in the copolymer was 21 mol%, and the content of cis-1, 4-structure of polyisoprene segments was 97.1 wt%.
Example 6
To a 500mL polymerization flask were added 0.062mmol of the rare earth complex P1 and 10mL of xylene, followed by 1.24mmol of triisobutylaluminum and 1.86mmol of ethylaluminoxane, and mixed at 25 ℃ for 10 min. 300mL of an isoprene hexane solution (58 mmol of isoprene monomer) was added to the polymerization flask, and the mixture was reacted at 25 ℃ for 130min with stirring. Then 30mmol of butyrolactone monomer is added, the temperature is raised to 70 ℃, and the reaction is continued for 6 h. The reaction was then quenched by the addition of 1mL of a 10% by volume solution of concentrated HCl in ethanol, the reaction solution was treated with ethanol, and the white polymer that had settled out was dried in a vacuum oven at 40 ℃ for 48 h. The total conversion was found to be 72%, the content of the butyrolactone segment in the copolymer was 23 mol%, and the content of the polyisoprene segment cis-1, 4-structure was found to be 97.2% by weight.
Example 7
This example was carried out in a similar manner to example 1, except that the same molar amount of rare earth complex P5 was used in place of the rare earth complex P1 in example 1. The rest is the same as in example 1. A white copolymer was obtained.
As a result: the total conversion was found to be 77.2%, the content of butyrolactone segment in the copolymer was 24 mol%, and the content of cis-1, 4-structure of polyisoprene segment was 97.0% by weight.
Example 8
This example was carried out in a similar manner to example 1, except that the same molar amount of rare earth complex P6 was used in place of the rare earth complex P1 in example 1. The rest is the same as in example 1. A white copolymer was obtained.
As a result: the total conversion was found to be 76.4%, the content of butyrolactone segments in the copolymer was 23.7 mol%, and the content of cis-1, 4-structure of polyisoprene segments was 97.2 wt%.
From the above results, it can be seen that the catalyst composition for olefin polymerization provided by the present invention is capable of catalyzing both homopolymerization and copolymerization of conjugated dienes. Moreover, the catalyst composition for olefin polymerization has high monomer conversion rate and high cis-structure content in the polymer when used for catalyzing homopolymerization and copolymerization of conjugated diene monomers.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (17)
1. A catalyst composition for olefin polymerization contains a main catalyst and a cocatalyst, wherein the main catalyst is a bis-Schiff base rare earth complex which has a structure shown in a formula (1), the cocatalyst comprises an alkylating reagent and/or an organic boron compound,
wherein R is1And R2Each independently selected from C1-6Alkyl and C1-6A group of at least one of alkoxy groups of (a);
ln is praseodymium element, neodymium element, samarium element, yttrium element, gadolinium element or scandium element.
2. The composition according to claim 1, wherein, in formula (1),
R1and R2Each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, primary butoxy, sec-butoxy and tert-butoxy;
ln is praseodymium element, neodymium element, samarium element, yttrium element, gadolinium element or scandium element.
3. The composition according to claim 1, wherein, in formula (1),
R1and R2Each independently selected from at least one member of the group consisting of methyl, ethyl, n-propyl, isopropyl, primary butyl, methoxy, ethoxy, n-propoxy, isopropoxy, and primary butoxy;
ln is neodymium element, yttrium element or gadolinium element.
4. The composition according to claim 1, wherein, in formula (1),
R1and R2Groups each independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, and primary butyl;
ln is neodymium element, yttrium element or gadolinium element.
5. The composition of any one of claims 1-4, wherein the alkylating agent is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylbenzylaluminum, diethylaluminum hydride, dibutylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, dibenzylaluminum hydride, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane.
6. The composition as claimed in any one of claims 1 to 4, wherein the cocatalyst is an alkylating agent or an organoboron compound, and the molar ratio of the content of the main catalyst in terms of rare earth metal elements to the content of the cocatalyst is 1: (0.1-100).
7. The composition of any of claims 1-4, wherein the co-catalyst is an alkylating agent and an organoboron compound; the molar ratio of the content of the main catalyst calculated by rare earth metal elements to the content of the alkylating agent and the organoboron compound is 1: (1-100): (0.1-3).
8. The composition of claim 6, wherein the cocatalyst is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylbenzylaluminum, and the molar ratio of the content of the procatalyst in terms of rare earth metal elements to the content of the cocatalyst is 1: (5-100).
9. The composition as claimed in claim 6, wherein the cocatalyst is an organic boron compound, and the molar ratio of the content of the main catalyst in terms of rare earth metal elements to the content of the cocatalyst is 1: (0.5-3).
10. Use of the catalyst composition for olefin polymerization according to any one of claims 1 to 9 for catalyzing the polymerization of conjugated diene monomer.
11. A method of polymerizing conjugated diene monomer, the method comprising: a method for polymerizing an olefin, comprising contacting a starting material comprising a conjugated diene monomer with a catalyst composition in the presence of a solvent to carry out a polymerization reaction, wherein the catalyst composition is the catalyst composition for olefin polymerization according to any one of claims 1 to 9.
12. The method of claim 11, wherein the polymerization conditions comprise: the temperature is from minus 30 ℃ to plus 100 ℃, and the time is from 10min to 24 h.
13. The method of claim 11, wherein the polymerization conditions comprise: the temperature is between 25 ℃ below zero and 80 ℃ above zero, and the time is between 30min and 12 h.
14. The method of any one of claims 11-13, wherein the solvent is selected from C5-10Alkane, C5-10At least one of cycloalkane of (a), benzene, toluene, xylene, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, dichlorobenzene, and tetrahydronaphthalene.
15. The method of any of claims 11-13, wherein the polymerization reaction is at least one of a copolymerization of a conjugated diene monomer with a polar monomer and a homopolymerization of a conjugated diene monomer, the polar monomer being at least one of caprolactone, butyrolactone, valerolactone, lactide, propylene oxide, and cyclohexene oxide.
16. The method of any of claims 11-13, wherein the conjugated diene monomer is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, and 2, 3-dimethylbutadiene.
17. The method of any one of claims 11-13, wherein the conjugated diene monomer is butadiene and/or isoprene.
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