CN109535286A - Early transition metal compound and preparation method and catalyst for olefines polymerizing composition and application and the method for preparing olefin polymer - Google Patents
Early transition metal compound and preparation method and catalyst for olefines polymerizing composition and application and the method for preparing olefin polymer Download PDFInfo
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- CN109535286A CN109535286A CN201710864791.6A CN201710864791A CN109535286A CN 109535286 A CN109535286 A CN 109535286A CN 201710864791 A CN201710864791 A CN 201710864791A CN 109535286 A CN109535286 A CN 109535286A
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- 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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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Abstract
The present invention relates to catalyst fields, disclose early transition metal compound and preparation method and catalyst for olefines polymerizing composition and application and the method for preparing olefin polymer, which has structure shown in formula (1) or formula (2).Catalyst containing provided by the invention nitrogenous and phosphine early transition metal compound has the advantages that catalytic activity is high, catalyst is at low cost.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to the nitrogenous early transition metal compound with phosphine of one kind, a kind of system
The method of standby nitrogenous and phosphine early transition metal compound and the early transition metal for the nitrogenous and phosphine being prepared by this method
Close object, a kind of catalyst for olefines polymerizing composition, catalyst for olefines polymerizing composition catalysis ethylene homo reaction and/or
Application and a kind of method for preparing olefin polymer in ethylene-alpha-olefin copolyreaction.
Background technique
Polyolefin is to be widely used and very important a kind of high molecular material, includes ethylene, the homopolymer of alhpa olefin and altogether
Polymers.Polyolefin is with a very important position in synthetic resin industry, can be used as film, tubing, wire and cable and uses.
The progress of olefin polymerization catalysis technology is the direct driving force of polyolefin industry technological progress.From traditional
Single active center's metallocene catalyst that Ziegler-Natta catalyst occurs to late 1980s, then at the end of the 20th century
High activity " cyclopentadienyl after " and late transition metal catalyst, the catalytic polymerization of alkene be always the coke of researcher and production firm's concern
Point.
That there are catalytic activity is low for traditional Ziegler-Natta catalyst, and molecular weight distribution is wide, and polymerisation in solution obtains poly-
Close the disadvantage that remaining catalyst content is high in product.The discovery of 4th race's metallocene catalyst then preferably solves this and asks
Topic, due to single active center, enabling people to obtain expected structure as desired by the structure for changing catalyst
Polymer (W.Kaminsky etc., Adv.Organomet.Chem.1980,18,99；H.H.Brintzinger etc.,
Angew.Chem.Int.Ed.Engl.1995,34,1143).In recent ten years, to be replaced containing the ligand of the coordination atoms such as N, O, P
The metal complex that cyclopentadiene is obtained with transition-metal coordination also flourishes as the research of olefin polymerization catalysis,
This kind of catalyst are collectively referred to as catalyst " after cyclopentadienyl ".
Late transition metal (Fe, Co, Ni, Pd etc.) catalyst can obtain a variety of polyethylene products with catalyzed ethylene polymerization, such as
From the linear polyethylene to highly branched structure of height, from Unimodal Distribution to broad peak or the polyethylene and ethylene of bimodal distribution
With copolymer, the polyolefin block copolymer of polar monomer etc..
1998, Brookhart and Gibson respectively reported Fe, Co bis-imine pyridine complex (structure such as following formula institute
Show), to vinyl polymerization activity with higher under co-catalyst methylaluminoxane (MAO) activation, obtain linear high density
Polyethylene (HDPE).The study found that activity an order of magnitude generally higher than cobalt catalyst system of iron catalyst system.
US5557023 discloses the late transition metal compound of the amine containing phosphine with following general formula structure for alhpa olefin
Oligomerisation:
US6762258B2, which is disclosed, contains phosphine, nitrogen tridentate ligand Fe, Co, Ni pyridine complex with structure as follows,
In addition, US6133387 discloses late transition metal Fe, Co, Ni, Pd of double phosphinimines containing pyridine, it is used to the polymerization of alkene, but
Be both complex-catalyzed vinyl polymerizations activity only showed under specific reaction condition (such as high pressure) it is higher, therefore
It is unfavorable for the extensive use of the catalyst:
It is late transition metal complex using the olefin polymerization catalysis that the above-mentioned prior art provides.
Summary of the invention
The object of the present invention is to provide a kind of new olefin polymerization catalysis, are used for alkene homopolymerization or copolymerization, especially use
It is copolymerized in ethylene homo and ethylene and alhpa olefin, to which high density polyethylene (HDPE) and ethylene-can be obtained under flexible operating condition
Alhpa olefin elastomer.
The present inventor has found that the group ivb metal pyridine complex containing phosphine, nitrogen (monodentate ligand) exists under study for action
As catalyst for being catalyzed ethylene homo and ethylene and when alhpa olefin is copolymerized, can high activity in broad polymerizing condition
Lower acquisition high density polyethylene (HDPE) or ethylene-alpha-olefin elastomer.That is, the group ivb metal containing phosphine, nitrogen (monodentate ligand)
Pyridine complex is when as catalyst for being catalyzed ethylene homo and ethylene and alhpa olefin copolymerization, under various polymerizing conditions (i.e.
It is under not high reaction pressure), than containing phosphine, nitrogen bidentate ligand or group VIII metal pyridine containing phosphine, nitrogen tridentate ligand
Complex all has considerably higher catalytic activity.Accordingly, inventor completes technical solution of the present invention.
To achieve the goals above, the first aspect of the present invention provides a kind of nitrogenous and phosphine early transition metal compound,
The compound has structure shown in formula (1) or formula (2),
Wherein, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-20Alkyl, C1-20Alkoxy and halogen composition group base
Group；
R1、R2、R3And R4It is each independently selected from by H, C1-4Alkyl, C6-12Aryl and by C1-4Alkyl replace
C7-16Aryl composition group group；
Mt is group ivb metallic element；
X is the atom or group being bonded on Mt element, and X is selected from by C1-10Alkyl and halogen composition group in extremely
A kind of few group；N is integer, and meets the chemical valence of Mt bonding.
Second aspect, the present invention provide a kind of method of early transition metal compound for preparing nitrogenous and phosphine, this it is nitrogenous and
The early transition metal compound of phosphine has structure shown in formula (1),
This method comprises:
1) formula (13) compound represented in the presence of an organic, is carried out first with n-BuLi to react, obtains first
Lithium salts；
2) first lithium salts second is carried out with formula (11) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains chemical combination shown in formula (14)
The intermediate of object；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, determine in the definition and aforementioned first aspect of formula (1), formula (11), formula (13) and the substituent group in formula (14)
Justice is identical, and the X in formula (13)1For halogen, X2For the R in formula (1)4。
The third aspect, the present invention provide a kind of method of early transition metal compound for preparing nitrogenous and phosphine, this it is nitrogenous and
The early transition metal compound of phosphine has structure shown in formula (2),
This method comprises:
1) formula (11) and formula (12) compound represented in the presence of an organic, are carried out first with n-BuLi to react,
Obtain the first lithium salts；
2) first lithium salts second is carried out with formula (13) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains chemical combination shown in formula (15)
The intermediate of object；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, definition and the aforementioned first aspect of formula (2), formula (11), formula (12), formula (13) and the substituent group in formula (15)
In definition it is identical, and the X in formula (13)1And X2It is each independently halogen.
Fourth aspect, the present invention provide be prepared nitrogenous of the method as described in aforementioned second aspect and the third aspect and
The early transition metal compound of phosphine.
5th aspect, the present invention provide a kind of catalyst for olefines polymerizing composition, contain major catalyst in the composition
And activator, the major catalyst are nitrogenous described in aforementioned first aspect of the present invention and/or fourth aspect and phosphine preceding transition
Metallic compound, the activator include aluminum contained compound and optionally include organoboron compound.
6th aspect, the present invention provide catalyst for olefines polymerizing composition described in the 5th aspect in catalysis ethylene homo
Application in reaction and/or ethylene-alpha-olefin copolyreaction.
7th aspect, the present invention provide a kind of method for preparing olefin polymer, this method comprises: in the presence of solvent,
Catalyst for olefines polymerizing composition described in olefinic monomer and fifth aspect present invention is subjected to haptoreaction.
Catalyst containing the aforementioned early transition metal compound containing phosphine and nitrogen (monodentate ligand) provided by the invention has
The advantage that catalytic activity is high, catalyst is at low cost, and excellent catalytic activity is all had under wide in range polymeric reaction condition.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, of the inventionFirst aspectProvide a kind of nitrogenous and phosphine early transition metal compound, the chemical combination
Object has structure shown in formula (1) or formula (2),
Wherein, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-20Alkyl, C1-20Alkoxy and halogen composition group base
Group；
R1、R2、R3And R4It is each independently selected from by H, C1-4Alkyl, C6-12Aryl and by C1-4Alkyl replace
C7-16Aryl composition group group；
Mt is group ivb metallic element；
X is the atom or group being bonded on Mt element, and X is selected from by C1-10Alkyl and halogen composition group in extremely
A kind of few group；N is integer, and meets the chemical valence of Mt bonding.
The halogen of the invention includes fluorine, chlorine, bromine and iodine.
N X of the invention can be same or different.
The C1-20Alkyl refer to that the total number of carbon atoms is the alkyl of 1-20, such as can be C1、C2、C3、C4、C5、C6、C7、
C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkyl.For example, the C1-20Alkyl can be C1-20
Alkyl or C2-20Alkenyl.
The C1-20Alkoxy refer to that the total number of carbon atoms is the alkoxy of 1-20, such as can be C1、C2、C3、C4、C5、
C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkoxy.
The C1-4Alkyl refer to that the total number of carbon atoms is the alkyl of 1-4, such as can be C1、C2、C3Or C4Alkyl.Example
It such as can be C1-4Alkyl or C2-4Alkenyl.
The C6-12Aryl refer to that the total number of carbon atoms is the aryl of 6-12, such as can be phenyl, naphthalene or xenyl.
It is described by C1-4Alkyl replace C7-16Aryl refer to that the total number of carbon atoms is the aryl of 7-16, and on aryl
At least one H is by C1-4Alkyl replace, such as can be for by C1-4Alkyl replace phenyl, naphthalene, xenyl, anthryl or phenanthrene
Base.Such as it can be for by C1-4Alkyl and/or C2-4Alkenyl replace C7-16Aryl.
The group ivb metallic element is Ti, Zr or Hf.
According to the first preferred embodiment, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-16Alkyl, C1-16Alkoxy and halogen composition group base
Group；
R1、R2、R3And R4It is each independently selected from by H, C1-4Alkyl, C6-10Aryl and by C1-4Alkyl replace
C7-14Aryl composition group group；
Mt is Ti, Zr or Hf；
X is selected from by C1-8Alkyl, fluorine, chlorine, bromine and iodine composition at least one of group group.
According to second of preferred embodiment, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-10Alkyl, C1-10Alkoxy and halogen composition group base
Group；
R1、R2、R3And R4It is each independently selected from by H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzene
Base, naphthalene and the C replaced by least one of methyl, ethyl, n-propyl, isopropyl, normal-butyl and tert-butyl substituent group7-14
Aryl composition group group；
Mt is Ti, Zr or Hf；
X is selected in the group of free methyl, ethyl, n-propyl, isopropyl, cyclopentadiene, fluorine, chlorine, bromine and iodine composition at least
A kind of group.
According to the third preferred embodiment, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-6Alkyl, C1-6Alkoxy and halogen composition group base
Group；
R1、R2、R3And R4It is each independently selected from phenyl, naphthalene and by methyl, ethyl, n-propyl, isopropyl, normal-butyl
And the C that at least one of tert-butyl substituent group replaces7-14At least one of aryl group；
Mt is Ti, Zr or Hf；
Be all in halogen or n X one of n X is cyclopentadiene and remaining (n-1) a X is halogen.
In the present invention, it is preferred to which n is 2 or 3.
Nitrogenous and phosphine the early transition metal compound that the first aspect of the present invention provides is urged being formed together with activator
Agent and when being used for the polymerization reaction of catalyst alkene, have catalytic activity high and suitable for preparing high density polyethylene (HDPE) and ethylene-α
The advantages of olefin elastomer.
As previously mentioned, of the inventionSecond aspectProvide a kind of side for preparing nitrogenous and phosphine early transition metal compound
Method, nitrogenous and phosphine the early transition metal compound have structure shown in formula (1),
This method comprises:
1) formula (13) compound represented in the presence of an organic, is carried out first with n-BuLi to react, obtains first
Lithium salts；
2) first lithium salts second is carried out with formula (11) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains chemical combination shown in formula (14)
The intermediate of object；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, determine in the definition and aforementioned first aspect of formula (1), formula (11), formula (13) and the substituent group in formula (14)
Justice is identical, and the X in formula (13)1For halogen, X2For the R in formula (1)4。
As previously mentioned, of the inventionThe third aspectProvide a kind of side for preparing nitrogenous and phosphine early transition metal compound
Method, nitrogenous and phosphine the early transition metal compound have structure shown in formula (2),
This method comprises:
1) formula (11) and formula (12) compound represented in the presence of an organic, are carried out first with n-BuLi to react,
Obtain the first lithium salts；
2) first lithium salts second is carried out with formula (13) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains chemical combination shown in formula (15)
The intermediate of object；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, definition and the aforementioned first aspect of formula (2), formula (11), formula (12), formula (13) and the substituent group in formula (15)
In definition it is identical, and the X in formula (13)1And X2It is each independently halogen.
In the second aspect of the present invention and the third aspect, first reaction, the second reaction, third reaction and the 4th are anti-
The condition answered can include: that reaction temperature is subzero 80 DEG C to 200 DEG C above freezing each independently, and the reaction time is 0.1~30h.
In the second aspect of the present invention and the third aspect, it is preferable that in step 1), the organic solvent is selected from first
At least one of benzene, hexane, pentane, benzene, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane and tetrahydrofuran.
In the third aspect of the invention, under preferable case, the step 1) for example can be using including the following steps
Method carries out: formula (11) and formula (12) compound represented being dissolved in organic solvent, solution A is formed；Then it will contain n-
The solution B of BuLi is mixed to carry out described first and react with the solution A.
The organic solvent contained in the solution A be preferably toluene, pentane, benzene, dimethylbenzene, methylene chloride, chloroform,
At least one of tetrachloromethane and tetrahydrofuran；Solvent in the solution B is preferably hexane, pentane, benzene, dimethylbenzene, two
At least one of chloromethanes, chloroform, tetrachloromethane and tetrahydrofuran.
In the second aspect of the present invention and the third aspect, the first lithium salts obtained after first reaction of the invention can
It is reacted with entering directly into step 2), can also be re-introduced into step 2) and be reacted after isolating and purifying.This
To the step of isolating and purifying, there is no particular limitation for invention, and those skilled in the art can be using such as recrystallization, column chromatography
The method routinely applied is isolated and purified in the art.
In the third aspect of the invention, total dosage of the main material formed by formula (11) and formula (12) compound represented
Dosage molar ratio with n-BuLi is preferably 1:(0.5~1.5).
In the third aspect of the invention, it is preferable that the use of first lithium salts and the formula (13) compound represented
Amount molar ratio is 1:(0.1~1.2).
Preferably, in the second aspect of the present invention and the third aspect, the product and the trimethyl that step 2) obtains are folded
The dosage molar ratio of nitrogen silane is 1:(0.8~2).
Preferably, in step 4), it is 50~200 DEG C that the condition of the 4th reaction, which includes: reaction temperature, the reaction time
For 2~30h.Preferably, the resulting intermediate of step 3) and the MtX(n+1)Dosage molar ratio be 1:(1~2).
It can also include necessary post-processing step in each step of preceding method of the invention, those skilled in the art can
To be post-processed using various steps commonly used in the art, to purify the crude product of each step.Such as it is described after
Processing step may include except solvent processing, carrying out washing treatment and drying process etc..
As previously mentioned, of the inventionFourth aspectProvide the preceding transition gold for the nitrogenous and phosphine being prepared by preceding method
Belong to compound.
Nitrogenous and phosphine early transition metal compound described in the fourth aspect of the present invention and the first aspect of the present invention institute
The early transition metal compound beneficial effect having the same for the nitrogenous and phosphine stated.
As previously mentioned, of the invention5th aspectA kind of catalyst for olefines polymerizing composition is provided, in the composition
Containing major catalyst and activator, the major catalyst is nitrogenous described in aforementioned first aspect of the present invention and/or fourth aspect
With the early transition metal compound of phosphine, the activator includes aluminum contained compound and optionally includes organoboron compound.
According to the first preferred embodiment, the activator is aluminum contained compound, with the institute of elemental metal
The content molar ratio for stating major catalyst and the aluminum contained compound in terms of aluminium element is 1:(0.1~3000), more preferably 1:
(50~1000).
According to second of preferred embodiment, the activator be aluminum contained compound and organoboron compound, with
The major catalyst of elemental metal, the aluminum contained compound in terms of aluminium element and the organoboration in terms of boron element
The content molar ratio for closing object is 1:(5~500): (1~5), preferably 1:(5~200): (1~5).
Preferably, the aluminum contained compound is the mixture or alkyl aluminum of alkyl aluminum compound and alkyl aluminum compound
Siloxane compound.
Preferably, the institute in the mixture of the alkyl aluminum compound and alkyl aluminum compound, in terms of aluminium element
State the content molar ratio of the content of alkyl aluminum compound and the alkyl aluminum compound in terms of aluminium element for 1:(10~
500)；More preferably 1:(25~300).
Preferably, the alkyl aluminum compound has structure shown in formula (3),
Wherein, R31For at least one in methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl and tert-butyl
Kind group；T is the integer of 5-30.It is highly preferred that in formula (3), R31For selected from methyl, ethyl, n-propyl, isopropyl and tertiary fourth
At least one of base group.It is further preferred that in formula (3), R31For at least one in methyl, ethyl and isopropyl
Kind group.It is particularly preferred that the alkyl aluminum compound be methylaluminoxane (MAO) and/or isobutyl aluminium alkoxide,
That is, R31For methyl or isobutyl group.
Preferably, the alkyl aluminum compound be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three oneself
Base aluminium, dimethylaluminum chloride, diethyl aluminum chloride, dipropyl aluminium chloride, diisobutyl aluminum chloride, dihexylaluminum chloride, methyl
Al dichloride, ethylaluminum dichloride, propyl al dichloride, isobutyl aluminium dichloride, hexyl al dichloride, dimethyl hydrogenated aluminium,
At least one of diethylaluminum hydride, dipropyl aluminum hydride, diisobutyl aluminium hydride and dihexyl aluminum hydride.Particularly preferably
Ground, the alkyl aluminum compound are triisobutyl aluminium.
Preferably, the organoboron compound is selected from three (pentafluorophenyl group) boron (B (C6F5)3), N, N- dimethyl puratized agricultural spray four
(pentafluorophenyl group) borate ([HNMe2Ph][B(C6F5)4]) and (pentafluorophenyl group) borate of triphen carbon four ([Ph3C][B
(C6F5)4At least one of]).
Other necessary additives can also be contained in the catalyst for olefines polymerizing composition of the invention, as long as this
A little additives will not influence the catalytic effect of the composition.For example, the composition can contain impurity scavenger.
The catalyst that the fifth aspect of the present invention provides is living with excellent catalysis during catalysed olefin polymerization
Property and the effect suitable for preparing high density polyethylene (HDPE) and ethylene-alpha-olefin elastomer.
As previously mentioned, of the invention6th aspectCatalyst for olefines polymerizing composition described in the 5th aspect is provided to exist
The application being catalyzed in ethylene homo reaction and/or ethylene-alpha-olefin copolyreaction.
It is suitable to the addition of each component formed in the catalyst for olefines polymerizing composition in the application of the invention
There is no particular limitation for sequence and Adding Way, can be by major catalyst, activator and optionally after the additive that contains mixes in advance
It is added in polymerization reaction, major catalyst, activator and the optionally additive that contains can also be added separately to polymerization reaction
In.According to a kind of preferred embodiment: the additive first contained by activator and optionally is added in reaction system, then
It is passed through olefinic monomer, then adds major catalyst.
As previously mentioned, of the invention7th aspectA kind of method for preparing olefin polymer is provided, this method comprises:
In the presence of solvent, olefinic monomer contact instead with catalyst for olefines polymerizing composition described in fourth aspect present invention
It answers.
Preferably, it is subzero 50 DEG C to 200 DEG C above freezing that the catalytic condition, which includes: temperature, the time for 0.1~
6h, pressure are 0.1~5MPa；It is highly preferred that it is 20~100 DEG C that the catalytic condition, which includes: temperature, the time 0.2
~5h, pressure are 0.1~2MPa.It is gauge pressure in the pressure.
The haptoreaction of the invention can be carried out using polymerisation in solution or bulk polymerization mode.Polymerization of the invention is anti-
Should can be solution polymerization, those skilled in the art it will of course be appreciated that solvent used in it in homopolymerization condition
Under should be in a liquid state, and cannot participate in polymerization reaction, will not react with the polymer reacted, i.e., the solvent is
It is inert.This kind of solvent is it will be apparent that and can be easy to carry out for the those of ordinary skill of polymerization field
Selection.Nevertheless, for the purpose of the present invention, the specific example of the organic solvent for example can be benzene, toluene, ethylbenzene, diformazan
One of benzene, pentane, n-hexane, heptane, octane and hexamethylene are a variety of, preferably n-hexane, octane or heptane, more preferably
Use n-hexane as the solvent in homopolymerization of the invention.For polymerization reaction of the invention, the use of the solvent
Amount is so that the concentration of polymer is 5~30 weight %, in the range of preferably 8~10 weight %.
According to the present invention, above-mentioned polymerization process preferably carries out under inert atmosphere protection, such as can use nitrogen, helium
One of gas, argon gas etc. a variety of provide such inert atmosphere.
In polymerization reaction of the invention, terminator can be used after completion of the polymerization reaction and terminate polymerization reaction.For
The terminator of this step is conventional to those skilled in the art.The terminator that usually can be used includes deionization
Water, alcohol, acid etc..In the present invention, it is preferred to which the terminator used is one of isopropanol, methanol, water etc. or a variety of.
Preferably, the olefinic monomer is ethylene and/or alpha-olefin.Preferably, the alpha-olefin be propylene, 1- butylene,
1- amylene, 1- hexene, 1- octene, 4-methyl-1-pentene, cyclopentene, cyclohexene, norbornene, 1- methyinorbornene, 5- first
At least one of base norbornene, dicyclopentadiene, 5- methylene -2- norbornene and 5- ethylidene -2- norbornene.
Particularly, high catalytic efficiency can be reached by the olefin polymerization that aforementioned catalytic agent of the invention is catalyzed, together
When obtain ethylene-alpha-olefin elastomer.The method for preparing ethylene-alpha-olefin copolymer of the invention is easy to operate, catalyst cost
It is lower.
More specifically, above-mentioned preparation method using composition of the invention as catalyst in the case where, can be with more
Ethylene propylene copolymer is made in high catalytic efficiency, such as catalytic efficiency can achieve 106G polymer/mol metal .h.
It below will the present invention will be described in detail by example.
In following preparation example, embodiment and comparative example, in case of no particular description, the various raw materials used come
From commercially available.
The weight average molecular weight and molecular weight distributing index (PDI=Mw/Mn) of polymer as described below are solidifying using Waters150
Glue penetration chromatography (GPC) measurement, and at 135 DEG C, it is measured with 1,2,4- trichloro-benzenes for mobile phase.
Catalytic efficiency refers to the quality of the resulting polymer of the Mt of unit mole, with unit g polymer/mol metal .h
It indicates.
Preparation example 1: ligand shown in preparation formula (A1), 2- (diphenylphosphino) pyridine
1) by 2- bromopyridine (0.01mol), the dilution in hexane (100mL) is added dropwise n-BuLi (6.25mL) at -78 DEG C
Hexane solution, react 1h；
2) at 25 DEG C, diphenylphosphine (0.01mmol) is dissolved in the toluene of 20mL, solution is to slowly warm up to 25
DEG C, the reaction was continued 2h obtains ligand shown in formula (A1).
Yield 83%；1H NMR(400MHz,C6D6) δ: 8.50 (d, J=4.6Hz, 1H, py), 7.52 (t, J=7.2Hz,
4H,o-PPh2),7.10–6.94(m,7H,m-PPh2,p-PPh2, py), 6.85 (t, J=7.6Hz, 1H, py), 6.48 (t, J=
6.0Hz,1H,py)
Preparation example 2: ligand shown in preparation formula (A2), 2- (Ph2P=NTMS) pyridine
By trimethyl azide silane N3SiMe3(0.02mol) is slowly added into 2- (diphenylphosphino) pyridine (0.01mol)
In the solution of 20mL toluene, reaction mixture is heated to reflux 12h.Solvent and excessive TMSN are removed when vacuumizing3When, it obtains
To white solid, i.e. ligand shown in (A2).
Yield 96%；1H NMR(400MHz,C6D6)δ:8.38(m,1H,py),8.28(m,1H,py),7.98–7.87(m,
4H,o-PPh2),7.04–6.95(m,8H,m-PPh2,p-PPh2,py),6.45-6.41(m,1H,py),0.34(s,9H,-
SiMe3)。
Preparation example 3: preparation formula (1A) compound represented
Ligand (5mmol) shown in formula (A2) that preparation example 2 is prepared is dissolved in 10mL toluene, is stirred evenly,
The toluene solution for containing cyclopentadiene titanium trichloride (5mmol) to addition 5mL, is heated to 110 DEG C, reacts 12h, is subsequently cooled to
25℃。
Preparation example 4: ligand shown in preparation formula (B1)
1) at -78 DEG C, to the diphenylphosphine (PHPh of the THF (100mL) of stirring2) (0.02mol) middle addition n-BuLi
(hexane solution of 12.5mL, 1.6M), obtains dark red solution, stirs 8h at 25 DEG C；
2) THF solution that 2, the 6- dibromo pyridine (0.01mol) of 20mL is added dropwise in solution is stated then up, and mixture is stirred
After mixing 8h, removing solvent is vacuumized, obtains ligand shown in formula (B1).
Yield 78%；1H NMR(400MHz,C6D6)δ:7.44(m,8H,o-PPh2),7.02(m,12H,m-PPh2,p-
PPh2), 6.94 (d, J=8.4Hz, 2H, py), 6.73 (m, 1H, py).
Preparation example 5: ligand shown in preparation formula (B2)
By trimethyl azide silane N3SiMe3(0.02mol) is slowly added into 2,6- bis- (diphenylphosphino) pyridine
In the solution of (0.01mol) and 20mL toluene, reaction mixture is heated to reflux 12h.Solvent and excessive is removed when vacuumizing
TMSN3When, obtain white solid, i.e. ligand shown in formula (B2).
Yield 86%；1H NMR(400MHz,CDCl3)δ:8.45-8.37(m,2H,py),8.05-7.97(m,1H,py),
7.51–7.43(m,12H,m-PPh2,p-PPh2),7.27–7.22(m,8H,o-PPh2),0.01(s,18H,-SiMe3).
Preparation example 6: preparation formula (1B) compound represented
Ligand (5mmol) shown in formula (B2) that preparation example 5 is prepared is dissolved in 10mL toluene, is stirred evenly,
The toluene solution for containing cyclopentadiene titanium trichloride (10mmol) to addition 5mL, is heated to 110 DEG C, reacts 12h, then cools down
To 25 DEG C.
Preparation example 7: preparation formula (2A) compound represented
Ligand (5mmol) shown in formula (A2) that preparation example 2 is prepared is dissolved in 10mL toluene, is stirred evenly,
The toluene solution for containing titanium trichloride (5mmol) to addition 5mL, is heated to 100 DEG C, reacts 15h, is subsequently cooled to 25 DEG C.
Preparation example 8: preparation formula (2B) compound represented
Ligand (5mmol) shown in formula (B2) that preparation example 5 is prepared is dissolved in 10mL toluene, is stirred evenly,
The toluene solution for containing titanium trichloride (10mmol) to addition 5mL, is heated to 120 DEG C, reacts 10h, is subsequently cooled to 25 DEG C.
Using method preparation formula (3A) compound represented similar with aforementioned preparation example, formula (3B) compound represented,
Formula (4A) compound represented and formula (4B) compound represented are only that the type of raw material is different.
Embodiment 1: ethylene propylene copolymer (MAO is as activator)
Under nitrogen protection and at 50 DEG C, the toluene solution that the MAO of 2mL is added into the toluene of 150mL (is purchased from
Albemarle company, similarly hereinafter；The dosage of the toluene solution of MAO make Al content be 10 μm of ol/mL) and be continuously passed through ethylene/
Propylene/hydrogen mixed gas (molar ratio 1:1.5:0.05, volume flow 50L/h) simultaneously keep gauge pressure be 0.6MPa, then plus
Enter formula (1A) compound represented (0.03mmol), polymerize 15min, stops supply monomer.It is terminated and is reacted using isopropanol, and added
Enter anti-aging agent such as lrganox 1520 (dosage makes the content of anti-aging agent in polymer be 0.2 weight %, is purchased from BASF AG,
Similarly hereinafter).Obtained polymer is removed into solvent, oven drying.
As a result as shown in table 1.
Embodiment 2: ethylene propylene copolymer (MAO and organoboron compound are as activator)
Under nitrogen protection and at 70 DEG C, the toluene solution that the MAO of 0.5mL is added into the toluene of 150mL (is purchased from
Albemarle company, similarly hereinafter；The dosage of the toluene solution of MAO make Al content be 10 μm of ol/mL) and be continuously passed through ethylene/
Propylene/hydrogen mixed gas (molar ratio 1:1.5:0.01, volume flow 50L/h) simultaneously keeps gauge pressure for 0.6MPa, is added
[CPh3][B(C6F5)4] compound cocatalyst B/Ti=1/1 (molar ratio) (being dissolved in toluene solution), formula is then added
(1B) compound represented (0.02mmol) polymerize 15min, stops supply monomer.It is terminated and is reacted using isopropanol, and be added anti-
Old agent such as lrganox 1520 (dosage makes the content of anti-aging agent in polymer be 0.2 weight %).Obtained polymer is removed
Remove solvent, oven drying.
As a result as shown in table 1.
Embodiment 3: ethylene homo (MAO and organoboron compound are as activator)
Under nitrogen protection and at 50 DEG C, the toluene solution that the MAO of 0.5mL is added into the toluene of 150mL (is purchased from
Albemarle company, similarly hereinafter；The dosage of the toluene solution of MAO makes the content of Al be 10 μm of ol/mL) and continuously it is passed through ethylene
Gas volumetric flow is 50L/h) and keep gauge pressure for 0.6MPa, [CPh is added3][B(C6F5)4] compound cocatalyst B/Ti=
Formula (2A) compound represented (0.02mmol) is then added in 1/1 (molar ratio) (being dissolved in toluene solution), polymerize 15min,
Stop supply monomer.It is terminated and is reacted using isopropanol, obtained polymer is removed into solvent, oven drying.
As a result as shown in table 1.
Embodiment 4: ethylene homo (MAO is as activator)
Under nitrogen protection and at 50 DEG C, the toluene solution that the MAO of 2mL is added into the toluene of 150mL (is purchased from
Albemarle company, similarly hereinafter；The dosage of the toluene solution of MAO makes the content of Al be 10 μm of ol/mL) and continuously it is passed through ethylene
Gas, volume flow 50L/h) and keep gauge pressure for 0.6MPa, formula (2B) compound represented (0.03mmol) is then added, gathers
15min is closed, supply monomer is stopped.It is terminated and is reacted using isopropanol, obtained polymer is removed into solvent, oven drying.
As a result as shown in table 1.
Embodiment 5: ethylene propylene copolymer (MAO is as activator)
The present embodiment is carried out using method similar to Example 1, the difference is that the present embodiment uses the formula of equal quantities
Formula (1A) compound represented in (2A) compound represented alternative embodiment 1.
Remaining is in the same manner as in Example 1.
As a result as shown in table 1.
Embodiment 6: ethylene propylene copolymer (MAO and organoboron compound are as activator)
The present embodiment is carried out using method similar to Example 2, the difference is that the present embodiment uses the formula of equal quantities
Formula (1B) compound represented in (2B) compound represented alternative embodiment 2.
Remaining is in the same manner as in Example 2.
As a result as shown in table 1.
Embodiment 7
The present embodiment is carried out using method similar to Example 3, the difference is that the present embodiment uses the formula of equal quantities
Formula (2A) compound represented in (3A) compound represented alternative embodiment 3.
Remaining is in the same manner as in Example 3.
As a result as shown in table 1.
Embodiment 8
The present embodiment is carried out using method similar to Example 4, the difference is that the present embodiment uses the formula of equal quantities
Formula (2B) compound represented in (3B) compound represented alternative embodiment 4.
Remaining is in the same manner as in Example 4.
As a result as shown in table 1.
Embodiment 9
The present embodiment is carried out using method similar to Example 3, the difference is that the present embodiment uses the formula of equal quantities
Formula (2A) compound represented in (4A) compound represented alternative embodiment 3.
Remaining is in the same manner as in Example 3.
As a result as shown in table 1.
Embodiment 10
The present embodiment is carried out using method similar to Example 4, the difference is that the present embodiment uses the formula of equal quantities
Formula (2B) compound represented in (4B) compound represented alternative embodiment 4.
Remaining is in the same manner as in Example 4.
As a result as shown in table 1.
Comparative example 1
This comparative example is carried out using method similar to Example 1, the difference is that this comparative example is using equal quantities
Formula (1A) institute in complex disclosed in the embodiment 21 of US6133387 (following name are as follows: complex 21) alternative embodiment 1
The compound shown.
Remaining is in the same manner as in Example 1.
As a result as shown in table 1.
Comparative example 2
This comparative example is carried out using method similar to Example 3, the difference is that this comparative example matching using equal quantities
Close formula (2A) compound represented in object 21 (complex disclosed in the embodiment 21 of US6133387) alternative embodiment 3.
Remaining is in the same manner as in Example 3.
As a result as shown in table 1.
Table 1
| Catalyst | Polymerization activity/× 105G polymer/mol metal .h | Mw/×104 | Tg/℃ | Tm/℃ | |
| Embodiment 1 | 1A | 9.8 | 22.1 | -47 | - |
| Embodiment 2 | 1B | 22.5 | 23.4 | -45 | - |
| Embodiment 3 | 2A | 10.2 | 52.3 | - | 135.1 |
| Embodiment 4 | 2B | 8.4 | 50.03 | - | 136 |
| Embodiment 5 | 2A | 9.5 | 18.6 | -46 | - |
| Embodiment 6 | 2B | 9.2 | 20.3 | -45 | - |
| Embodiment 7 | 3A | 9.1 | 56.1 | - | 134 |
| Embodiment 8 | 3B | 9.5 | 55.7 | - | 136 |
| Embodiment 9 | 4A | 10.0 | 65.3 | - | 137.2 |
| Embodiment 10 | 4B | 9.6 | 57.6 | - | 135.5 |
| Comparative example 1 | Complex 21 | 3.2 | 29.6 | - | 112.3 |
| Comparative example 2 | Complex 21 | 2.7 | 35.4 | - | 131.6 |
Can be seen that by the result of table 1 use catalyst provided by the invention can in broad range with compared with
High catalytic activity obtains Alathon and ethylene-alpha-olefin copolymer elastomer, and particularly, catalyst provided by the invention is
It is the also catalytic activity with higher under lower reaction pressure.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of nitrogenous and phosphine early transition metal compound, the compound have structure shown in formula (1) or formula (2),
Wherein, in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-20Alkyl, C1-20Alkoxy and halogen composition group group；
R1、R2、R3And R4It is each independently selected from by H, C1-4Alkyl, C6-12Aryl and by C1-4Alkyl replace C7-16's
The group of the group of aryl composition；
Mt is group ivb metallic element；
X is the atom or group being bonded on Mt element, and X is selected from by C1-10Alkyl and halogen composition group at least one
Kind group；N is integer, and meets the chemical valence of Mt bonding.
2. compound according to claim 1, wherein in formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-16Alkyl, C1-16Alkoxy and halogen composition group group；
R1、R2、R3And R4It is each independently selected from by H, C1-4Alkyl, C6-10Aryl and by C1-4Alkyl replace C7-14's
The group of the group of aryl composition；
Mt is Ti, Zr or Hf；
X is selected from by C1-8Alkyl, fluorine, chlorine, bromine and iodine composition at least one of group group；
Preferably,
In formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-10Alkyl, C1-10Alkoxy and halogen composition group group；
R1、R2、R3And R4It is each independently selected from by H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, phenyl, naphthalene
Base and the C replaced by least one of methyl, ethyl, n-propyl, isopropyl, normal-butyl and tert-butyl substituent group7-14Virtue
The group of the group of base composition；
Mt is Ti, Zr or Hf；
X selects at least one of free methyl, ethyl, n-propyl, isopropyl, cyclopentadiene, fluorine, chlorine, bromine and group of iodine composition
Group；
Preferably,
In formula (1) and formula (2),
R1、R2、R3And R4It is each independently selected from by H, C1-6Alkyl, C1-6Alkoxy and halogen composition group group；
R1、R2、R3And R4It is each independently selected from phenyl, naphthalene and by methyl, ethyl, n-propyl, isopropyl, normal-butyl and tertiary fourth
The C that at least one of base substituent group replaces7-14At least one of aryl group；
Mt is Ti, Zr or Hf；
Be all in halogen or n X one of n X is cyclopentadiene and remaining (n-1) a X is halogen.
3. a kind of method for preparing nitrogenous and phosphine early transition metal compound, which has
There is structure shown in formula (1),
This method comprises:
1) formula (13) compound represented in the presence of an organic, is carried out first with n-BuLi to react, obtains the first lithium salts；
2) first lithium salts second is carried out with formula (11) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains formula (14) compound represented
Intermediate；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, the definition of substituent group in formula (1), formula (11), formula (13) and formula (14) and determining in preceding claims 1 or 2
Justice is identical, and the X in formula (13)1For halogen, X2For the R in formula (1)4。
4. a kind of method for preparing nitrogenous and phosphine early transition metal compound, which has
There is structure shown in formula (2),
This method comprises:
1) formula (11) and formula (12) compound represented in the presence of an organic, are carried out first with n-BuLi to react, obtained
First lithium salts；
2) first lithium salts second is carried out with formula (13) compound represented to react；
3) product that step 2) obtains is carried out third with trimethyl azide silane to react, obtains formula (15) compound represented
Intermediate；
4) by the resulting intermediate of step 3) and MtX(n+1)Carry out the 4th reaction；
Wherein, the definition and preceding claims 1 or 2 of formula (2), formula (11), formula (12), formula (13) and the substituent group in formula (15)
In definition it is identical, and the X in formula (13)1And X2It is each independently halogen.
5. the method according to claim 3 or 4, wherein in step 1), the organic solvent is selected from toluene, hexane, penta
At least one of alkane, benzene, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane and tetrahydrofuran.
6. the method according to claim 3 or 4, wherein in step 4), the condition of the 4th reaction includes: reaction
Temperature is 50~200 DEG C, and the reaction time is 2~30h.
7. the early transition metal compound for the nitrogenous and phosphine that the method as described in any one of claim 3-6 is prepared.
8. a kind of catalyst for olefines polymerizing composition, major catalyst and activator, the major catalyst are contained in the composition
For nitrogenous and phosphine early transition metal compound described in any one of claim 1,2 and 7, the activator includes containing aluminium
Compound and optionally include organoboron compound.
9. composition according to claim 8, wherein the activator is aluminum contained compound, with the institute of elemental metal
The content molar ratio for stating major catalyst and the aluminum contained compound in terms of aluminium element is 1:(0.1~3000), preferably 1:(50
~1000)；Preferably,
The activator is aluminum contained compound and organoboron compound, with the major catalyst of elemental metal, with aluminium element
The aluminum contained compound of meter and the content molar ratio of the organoboron compound in terms of boron element are 1:(5~500): (1~
5), preferably 1:(5~200): (1~5).
10. composition according to claim 8 or claim 9, wherein the aluminum contained compound is alkyl aluminum compound and alkyl aluminum
The mixture or alkyl aluminum compound of siloxane compound, the preferably described alkyl aluminum compound be methylaluminoxane and/
Or isobutyl aluminium alkoxide, the alkyl aluminum compound be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three oneself
Base aluminium, dimethylaluminum chloride, diethyl aluminum chloride, dipropyl aluminium chloride, diisobutyl aluminum chloride, dihexylaluminum chloride, methyl
Al dichloride, ethylaluminum dichloride, propyl al dichloride, isobutyl aluminium dichloride, hexyl al dichloride, dimethyl hydrogenated aluminium,
At least one of diethylaluminum hydride, dipropyl aluminum hydride, diisobutyl aluminium hydride and dihexyl aluminum hydride；Preferably,
The organoboron compound is selected from three (pentafluorophenyl group) boron, N, four (pentafluorophenyl group) borate of N- dimethyl puratized agricultural spray and triphen
At least one of carbon four (pentafluorophenyl group) borate.
11. catalyst for olefines polymerizing composition described in any one of claim 8-10 is in catalysis ethylene homo reaction
And/or the application in ethylene-alpha-olefin copolyreaction.
12. a kind of method for preparing olefin polymer, this method comprises: in the presence of solvent, by olefinic monomer and claim
Catalyst for olefines polymerizing composition described in any one of 8-10 carries out haptoreaction；Preferably,
The catalytic condition includes: that temperature is subzero 50 DEG C to 200 DEG C above freezing, and the time is 0.1~6h, pressure 0.1
~5MPa.
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| CN115734975A (en) * | 2020-06-29 | 2023-03-03 | 宝理塑料株式会社 | Method for producing cyclic olefin copolymer, and catalyst composition for copolymerization of norbornene monomer and ethylene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110964049A (en) * | 2019-12-20 | 2020-04-07 | 万华化学集团股份有限公司 | Transition metal compound, olefin polymerization catalyst composition containing same, preparation method and application |
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| CN115734975A (en) * | 2020-06-29 | 2023-03-03 | 宝理塑料株式会社 | Method for producing cyclic olefin copolymer, and catalyst composition for copolymerization of norbornene monomer and ethylene |
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| CN115734975B (en) * | 2020-06-29 | 2024-02-27 | 宝理塑料株式会社 | Process for producing cyclic olefin copolymer, and catalyst composition for copolymerization of norbornene monomer and ethylene |
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