CN108359039A - A kind of copolymerization process of ethylene and end alkenyl silanes/siloxanes - Google Patents
A kind of copolymerization process of ethylene and end alkenyl silanes/siloxanes Download PDFInfo
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Abstract
The invention belongs to olefin-copolymerizations to react field, provide a kind of copolymerization process of ethylene and end alkenyl silanes/siloxanes, and this method includes：In the presence of carbon monoxide-olefin polymeric, ethylene is set to carry out copolymerization with end alkenyl silanes/siloxanes, the carbon monoxide-olefin polymeric includes major catalyst, co-catalyst and optional chain-transferring agent, and major catalyst is selected from least one of complex, wherein R shown in formula (I)1~R10It is each independently selected from hydrogen, saturated or unsaturated alkyl, oxyl etc.；M is selected from VIII race's metal, and X is halogen.Carbon monoxide-olefin polymeric used by the method for the present invention has higher polymerization activity in ethylene is reacted with end alkenyl silanes/copolymeric siloxane, can improve the content of comonomer, methyl on polymer molecular chain, have wide prospects for commercial application.
Description
Technical field
The invention belongs to olefin-copolymerizations to react field, and in particular, to a kind of ethylene with hold being total to for alkenyl silanes/siloxanes
Poly- method.
Background technology
Olefin copolymer containing vinyl silanes or silicone derivative group can apply to multiple fields, such as each
CABLE MATERIALS, tubing, adhesive, liner and the foamed products of cross-linked of type use.Vinyl silanes class group can pass through two kinds of sides
Method is linked on olefin polymer：A kind of method is to make alkene and vinyl silanes class chemical combination under radical initiator catalysis
Object forms (such as US 3225018) through high temperature, high pressure copolymerisation, and this polymerization technique is similar to ethylene high pressure homopolymerization, gained copolymer
Structure is similar to the structure of low density polyethylene (LDPE)；Another method is that a kind of allyl-or vinyl-silane are grafted to one kind
On already present polyolefin (such as US 3646155), the advantages of grafting, is, no matter low density polyethylene (LDPE), high density polyethylene (HDPE) all
It can be grafted, but be required in addition using radical initiator greatly when the disadvantage is that being grafted, this also makes preparation process complicate.
In addition, radical initiator usage amount can cause grafting amount too low very little；The usage amount of radical initiator is too many, then can cause
Polymer is excessively crosslinked.If ethylene and end alkenyl silanes/siloxane group coordination polymerization can be catalyzed, polymerization work can be simplified
Skill, and content of the controllable end alkenyl silanes/siloxane group on polymer chain.
Currently, only a small amount of reported in literature is using transient metal complex catalyzed alkene and siliceous polar monomer (end alkene
Base silane/siloxanes) copolymerization.For example, patent document WO 03/044066A2 disclose the rear mistake using two teeth or tridentate ligand
Crossing metal complex can be such that ethylene is copolymerized with allyl-or vinyl-silane, however, this method need to use expensive change
Property methylaluminoxane (MMAO) be co-catalyst, and polymerize at 4.0~6.0MPa of higher vinyl polymerization pressure, resulting polymers
Molecular weight and the degree of branching it is relatively low.Dalton Transaction, 2015,44 (47):20745-20752 is sub- using pyridine two
Amine Fe-series catalyst is catalyzed propylene and the polar monomer copolymerization containing silicon, and this method still needs to use MMAO for co-catalyst, needs 30
DEG C 0 DEG C of even lower temperature polymerisation 16 hours, and polymerization activity is relatively low, and when temperature is higher, copolyreaction can not be carried out.
Invention content
In order to solve above-mentioned technical problem of the existing technology, the present invention provides a kind of ethylene with end alkenyl silanes/
The copolymerization process of siloxanes, the catalyst system in this method have higher polymerization activity, and the molecular weight of resulting polymers
Narrowly distributing, the molecular weight and the degree of branching of polymer can regulate and control in wider range.
The present invention provides the copolymerization process of a kind of ethylene and end alkenyl silanes/siloxanes, this method includes：In catalyst
In the presence of composition, ethylene is set to carry out copolymerization with end alkenyl silanes/siloxanes, wherein the carbon monoxide-olefin polymeric
Including major catalyst, co-catalyst and optional chain-transferring agent, the major catalyst is selected from complex shown in formula (I) at least
It is a kind of：
In formula (I), R1~R10It is identical or different, be each independently selected from hydrogen, saturated or unsaturated alkyl, oxyl or
Halogen；M is selected from VIII race's metal, and X is halogen.
Compared with the late transition metal complex catalyst system and catalyzing for routinely using two teeth or tridentate ligand, method of the invention is adopted
Carbon monoxide-olefin polymeric has higher polymerization activity in ethylene is reacted with the Coordination copolymerization of end alkenyl silanes/siloxanes,
And the molecular weight and the degree of branching of polymer can be regulated and controled, there is wide prospects for commercial application.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides the copolymerization process of a kind of ethylene and end alkenyl silanes/siloxanes, this method includes：In catalyst
In the presence of composition, ethylene is set to carry out copolymerization with end alkenyl silanes/siloxanes (comonomer), wherein described to urge
Agent composition includes major catalyst, co-catalyst and optional chain-transferring agent.
The major catalyst (that is, single site catalysts) is selected from least one of complex shown in formula (I)：
In formula (I), R1~R10It is identical or different, be each independently selected from hydrogen, saturated or unsaturated alkyl, oxyl or
Halogen；M is selected from VIII race's metal, and X is halogen.
The halogen is F, Br, Cl or I.
Preferably, R1~R10It is each independently selected from hydrogen, C1~C10Saturation or unsaturated alkyl, C1~C10Alkoxy
Or halogen.
C1~C10Saturation or unsaturated alkyl specifically include C1~C10Alkyl, C3~C10Naphthenic base, C2~C10Alkenyl, C2
~C10Alkynyl, C6~C10Aryl, C7~C10Aralkyl etc..
C1~C10Alkyl refers to C1~C10Straight chained alkyl or C3~C10Branched alkyl, non-limiting examples include：
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, new penta
Base, n-hexyl, n-heptyl, n-octyl and positive decyl.
C3~C10The example of naphthenic base can include but is not limited to：Cyclopropyl, cyclopenta, cyclohexyl, 4- methylcyclohexyls,
4- ethylcyclohexyls, 4- n-propyls cyclohexyl and 4- normal-butyl cyclohexyl.
C6~C10The example of aryl can include but is not limited to：Phenyl, 4- aminomethyl phenyls and 4- ethylphenyls.
C2~C10The example of alkenyl can include but is not limited to：Vinyl and allyl.
C2~C10The example of alkynyl can include but is not limited to：Acetenyl and propargyl.
C7~C10The example of aralkyl can include but is not limited to：Phenyl methyl, phenylethyl, phenyl n-propyl, phenyl
Normal-butyl, phenyl t-butyl and propyloxy phenyl base.
C1~C10The non-limiting examples of alkoxy include：Methoxyl group, ethyoxyl, propoxyl group etc..
It is highly preferred that R1~R10It is each independently selected from hydrogen, C1~C6Alkyl, C2~C6Alkenyl, C1~C6Alcoxyl
Base or halogen.
In formula (I), M such as can be nickel, iron, cobalt, palladium, preferably nickel.
A kind of preferred embodiment according to the invention, the major catalyst are selected from least one of following complex,
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl；
And in complex 1~22, R7~R10It is hydrogen, M is nickel.
In the present invention, complex shown in formula (I) can be prepared by the following method to obtain：
1) formula (I-I) compound represented A and aniline or substituted aniline are returned in solvent under the effect of the catalyst
Diimide ligand compound shown in formula (I-II) is made in stream：
2) by diimide ligand compound and MX shown in formula (I-II)2Or MX2Derivative carries out complexation reaction, obtains formula
(I) complex shown in；
Wherein, to R1~R10And the description of M, X with it is identical above, details are not described herein.
In step 1), the catalyst can be selected from least one of p-methyl benzenesulfonic acid, acetic acid and formic acid.The solvent can
Selected from least one of toluene, methanol, ethyl alcohol and acetonitrile.The molar ratio of the compound A and aniline or substituted aniline is
2 to 1 ︰ 3 of 1 ︰ 2 to 1 ︰ 10, preferably 1 ︰.The temperature of the reflux is 40~120 DEG C, preferably 65~110 DEG C；The reflux
Time is 0.5~7 day, preferably 1~2 day.It is preferred that the amount of the catalyst is 0.01~20mol% of compound A amounts.
The restriction of substituent group on the substituted aniline is such as R1~R10, but R1~R10It is asynchronously hydrogen, for example, institute
It can be 2,6- methylanilines, 2,6- diethylanilines, 2,6- diisopropyl anilines, 2,6- dimethyl -4- to state substituted aniline
It is one or more in bromo- aniline and 2,6- difluoroanilines.
In step 2), the diimide ligand compound and MX2Or MX2Derivative (such as nickel halogenide or nickel halogenide derivative)
Molar ratio can be 1 ︰, 1 to 1 ︰ 1.2.The nickel halogenide or nickel halogenide derivative can be selected from NiBr2、NiCl2、(DME)NiBr2
Or (DME) NiCl2, wherein DME is the abbreviation of dimethyl ether.The temperature of the complexation reaction can be 0~60 DEG C, the reaction time
For 0.5~12h.The complexation reaction carries out under the part of anhydrous and oxygen-free, for example, can under inert atmosphere (be usually nitrogen) into
Row.
In a particular embodiment, the synthesis of the complex may include following steps：
A) compound A and substituted aniline are flowed back 1 day in ethanol as catalyst using acetic acid, solvent are removed after filtering,
Residue is dissolved with dichloromethane, parlkaline aluminium oxide pillar, is eluted with petrol ether/ethyl acetate (20 ︰ 1), and second is divided into
Product removes solvent and obtains yellow solid；Or
B) compound A and substituted aniline are flowed back 1 day in toluene by catalyst of p-methyl benzenesulfonic acid, reaction solution steams
After dry, residue is dissolved with dichloromethane, parlkaline aluminium oxide pillar, is eluted with petrol ether/ethyl acetate (20 ︰ 1), second
It is divided into product, removes solvent and obtain yellow solid；
Above-mentioned yellow solid is determined as the diimide ligand compound by nuclear-magnetism, infrared and elemental analysis；
C) under inert gas protection, by (DME) NiCl2Or (DME) NiBr2Dichloromethane solution (1 ︰ 1 in molar ratio
To 1 ︰ 1.2) it is added drop-wise in the solution of diimide ligand compound, it is stirred at room temperature, precipitation, vacuum after filtering is washed with ether is precipitated
Dry, products therefrom elemental analysis, IR Characterization are determined as complex shown in formula (I).
In addition, the complex that following embodiment is related to is prepared with reference to above-mentioned synthetic method using corresponding raw material,
The present invention repeats no more.
In the present invention, the co-catalyst can be the conventional selection in olefin coordination polymerization reaction.Under preferable case, institute
It states co-catalyst and is selected from least one of alkylaluminoxane, aryl boron and borate.
The alkylaluminoxane is for example selected from methylaluminoxane (MAO) and/or modified methylaluminoxane (MMAO).
It is highly preferred that the co-catalyst is methylaluminoxane, in this way have not only carbon monoxide-olefin polymeric higher total
Poly- activity, moreover it is possible to reduce cost of material.
The aryl boron is substituted or unsubstituted phenyl boron, more preferably three pentafluorophenyl group boron.
The borate is preferably N, four (pentafluorophenyl group) borate of N- dimethyl puratized agricultural spray and/or four (pentafluorophenyl group) boric acid
Trityl group salt.
In the carbon monoxide-olefin polymeric, the molar ratio of M (such as nickel) can be in aluminium and the major catalyst in co-catalyst
For (10~100000) ︰ 1, preferably (10~10000) ︰ 1, more preferably (100~5000) ︰ 1；Or in the co-catalyst
The molar ratio of boron and M in the major catalyst can be (0.01~1000) ︰ 1, preferably (0.1~100) ︰ 1.
According to the present invention, the molecular weight of the selection of chain-transferring agent and the controllable resulting polymers of addition realizes polymer
Regulation and control of the molecular weight in wider range.The type of the chain-transferring agent is not particularly limited in the present invention, can be according to transition
The type of metal M is selected.
In one embodiment, the chain-transferring agent is selected from trialkylaluminium and/or dialkyl group zinc.
Preferably, the chain-transferring agent be selected from trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three just oneself
At least one of base aluminium, tri-n-octylaluminium, zinc methide and diethyl zinc.
In this embodiment, in the chain-transferring agent in aluminium and the major catalyst molar ratio of M can be (1~
10000) 1 ︰, preferably (1~1000) ︰ 1；Or in the chain-transferring agent in zinc and the major catalyst molar ratio of M be (1~
1000) 1 ︰.
The copolymerization process of the present invention can carry out in the following manner：In presence of organic solvent, in anhydrous and oxygen-free condition
Under, by the carbon monoxide-olefin polymeric and ethylene, end alkenyl silanes/silicone contact.Wherein, the major catalyst and co-catalyst
Equal catalytic components can be separately added into reactor, and reactor is added after can also being pre-mixed each component, suitable for adding
Sequence or mixed condition are not particularly limited.
The organic solvent can be selected from C3~C20Hydrocarbon solvent, specific example includes butane, iso-butane, pentane,
Alkane, heptane, octane, hexamethylene, toluene, dimethylbenzene etc..It is preferred that the organic solvent is toluene and/or hexane.
In the present invention, " end alkenyl " includes vinyl, alpha-olefin, and the double bond on group is located at one end of strand
Portion." end alkenyl silanes/siloxanes " refers to " end alkenyl silanes " and/or " end alkenyl siloxane ".
Specifically, end alkenyl silanes are selected from least one of compound shown in formula (II)：
Wherein, m, n are respectively 0 or positive integer, respectively preferably 0~20 integer.
The non-limiting example of the end alkenyl silanes includes：Vinyl trimethylsilane, vinyltriethylsilane, allyl
Base triethylsilane, three normal-butyl silane of allyl, 7- octenyl trimethyl silanes etc..
According to the present invention, end alkenyl siloxane is selected from least one of compound shown in formula (III)：
Wherein, p, q are respectively 0 or positive integer, respectively preferably 0~20 integer.
The non-limiting example of the end alkenyl siloxane includes：Vinyltrimethoxysilane, allyl trimethoxy silicon
Alkane, allyltriethoxysilane, 7- octenyl trimethoxy silanes etc..
The dosage of copolymerization process according to the invention, the end alkenyl silanes/siloxanes is 0.01~3000mmol/L, excellent
It is selected as 0.1~1000mmol/L, more preferably 1~500mmol/L.
According to the present invention, the dosage of the major catalyst can with 0.00001~10mmol/L, preferably 0.0001~
1mmol/L, more preferably 0.001~0.5mmol/L.
In the present invention, " mmol/L " refers to the concentration of material in the reactor.
According to the present invention, the temperature of the copolyreaction can be selected in wide range, such as can be -20 DEG C
To 200 DEG C, preferably 40~120 DEG C, more preferably 60~110 DEG C.
The present invention is not particularly limited the pressure of the copolyreaction, as long as monomer can be made to carry out Coordination copolymerization reaction
.From reducing cost and simplifying the angle of polymerization technique, in the reactor, the pressure 1 of optimal ethylene~
1000atm, further preferably 1~200atm, more preferably 1~50atm.
Carbon monoxide-olefin polymeric in the method for the present invention can be catalyzed to high activity monomer and carry out copolyreaction, therefore reacting can
It is completed in a short time, the time of the copolyreaction can be 10~120min, preferably 20~50min.
In addition, after the time for reaching the copolyreaction, method of the invention further includes terminating this instead using terminator
It answers, the terminator can be the compounds containing active hydrogen such as water, alcohol, acid and amine that coordination polymerization is routinely selected.In a kind of reality
It applies in mode, the methanol or ethanol solution that the terminator can be acidified for the hydrochloric acid of 5~20 volume %, i.e. alcohol/concentrated hydrochloric acid=
95/5~80/20 (volume ratio).
The complex that the method for the present invention uses can be used in combination with co-catalyst at low pressures and realize ethylene and end
The copolymerization of alkenyl silanes/siloxanes, even if the carbon monoxide-olefin polymeric remains to keep in high temperature (such as 90 DEG C or more)
Comonomer, i.e., be successfully introduced on polymer molecular chain by higher catalytic activity；This method can be realized to polymer molecule
The regulation and control of amount and the degree of branching, and the narrow molecular weight distribution of polymer can be used for preparing the ethylene and end alkenyl of different physical properties
The copolymer of silane/siloxane.
Below by embodiment, the present invention will be described in detail, but the present invention should not be limited by the examples.
In following embodiment and comparative example,
Using Si elements in PANalytical companies Axios-Advanced type X-ray fluorescence spectra analyzing polymers
Relative amount, wherein Si contents are higher, and the content of comonomer is higher；
Using the methyl content in 13C H NMR spectroscopy test polymers：In 400MHz Bruker Avance400 nuclear magnetic resonance
On spectrometer, using 13 probes of 10mm PASEX, analysis survey is carried out with 1,2,4- trichloro-benzenes dissolving polymer samples at 120 DEG C
Examination obtains, wherein methyl content is higher, and the degree of branching of polymer is higher；
The molecular weight and molecular weight distribution PDI (PDI=Mw/Mn) of polymer use PL-GPC220 using trichloro-benzenes as solvent
Measurement (standard specimen at 150 DEG C：PS, flow velocity：1.0mL/min, pillar：3×Plgel 10um M1×ED-B 300×
7.5nm)。
Embodiment 1
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume % hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 2
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 100 DEG C.Finally with 5 volume % salt
The ethanol solution of acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 3
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,10mL allyl front threes are made
Oxysilane (57.4mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume % salt
The ethanol solution of acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 4
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.2mL diethyl is added
Zinc (hexane solution of 1mol/L) makes Zn/Ni=20,5mL allyltrimethoxysilanis (28.7mmol) be protected at 70 DEG C
The ethylene pressure for holding 10atm, is stirred to react 30min.It is finally neutralized, is polymerize with the ethanol solution that 5 volume % hydrochloric acid are acidified
The performance parameter of object, polymerization activity and polymer is as shown in table 1.
Embodiment 5
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.5mL diethyl is added
Zinc (hexane solution of 1mol/L) makes Zn/Ni=50,5mL allyltrimethoxysilanis (28.7mmol) be protected at 70 DEG C
The ethylene pressure for holding 10atm, is stirred to react 30min.It is finally neutralized, is polymerize with the ethanol solution that 5 volume % hydrochloric acid are acidified
The performance parameter of object, polymerization activity and polymer is as shown in table 1.
Embodiment 6
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.3mg (10 μm of ol) complex 2 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume % hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 7
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.3mg (10 μm of ol) complex 2 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.5mL diethyl is added
Zinc (hexane solution of 1mol/L) makes Zn/Ni=50,5mL allyltrimethoxysilanis (28.7mmol) be protected at 70 DEG C
The ethylene pressure for holding 10atm, is stirred to react 30min.It is finally neutralized, is polymerize with the ethanol solution that 5 volume % hydrochloric acid are acidified
The performance parameter of object, polymerization activity and polymer is as shown in table 1.
Embodiment 8
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；8.7mg (10 μm of ol) complex 1 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume % hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 9
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；10.8mg (10 μm of ol) complex 8 is added, then vacuumize again and is replaced 3 times with ethylene；Inject the first of 500mL
Benzene adds 6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), makes Al/Ni=1000,5mL allyls three
Methoxy silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume %
The ethanol solution of hydrochloric acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 10
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；8.9mg (10 μm of ol) complex 14 is added, then vacuumize again and is replaced 3 times with ethylene；Inject the first of 500mL
Benzene adds 6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), makes Al/Ni=1000,5mL allyls three
Methoxy silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume %
The ethanol solution of hydrochloric acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 11
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL 7- octenyls three are made
Methoxy silane (17.8mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume %
The ethanol solution of hydrochloric acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 12
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.2mL diethyl is added
Zinc (hexane solution of 1mol/L), makes Zn/Ni=20,5mL 7- octenyl trimethoxy silanes (17.8mmol), at 70 DEG C,
The ethylene pressure for keeping 10atm, is stirred to react 30min.It is finally neutralized, is gathered with the ethanol solution that 5 volume % hydrochloric acid are acidified
The performance parameter of conjunction object, polymerization activity and polymer is as shown in table 1.
Embodiment 13
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.5mL diethyl is added
Zinc (hexane solution of 1mol/l), makes Zn/Ni=50,5mL 7- octenyl trimethoxy silanes (17.8mmol), at 70 DEG C,
The ethylene pressure for keeping 10atm, is stirred to react 30min.It is finally neutralized, is gathered with the ethanol solution that 5 volume % hydrochloric acid are acidified
The performance parameter of conjunction object, polymerization activity and polymer is as shown in table 1.
Embodiment 14
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL vinyl trimethoxies are made
Base silane (31.6mmol).At 70 DEG C, the ethylene pressure of 10atm is kept, 30min is stirred to react.Finally with 5 volume % hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 15
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethyls are made
Silane (22.1mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 70 DEG C.Finally with 5 volume % hydrochloric acid acid
The ethanol solution of change neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 16
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000 is made, 0.5mL diethyl is added
Zinc (hexane solution of 1mol/L) makes Zn/Ni=50,5mL allyl trimethyl silanes (22.1mmol) be kept at 70 DEG C
The ethylene pressure of 10atm, is stirred to react 30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, obtains polymer.
The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 17
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 40 DEG C.Finally with 5 volume % hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 18
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
6.5mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) is added, Al/Ni=1000,5mL allyl trimethoxies are made
Base silane (28.7mmol) keeps the ethylene pressure of 10atm, is stirred to react 30min at 120 DEG C.Finally with 5 volume % salt
The ethanol solution of acid acidification neutralizes, and obtains polymer, and the performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 19
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.9.8mg (10 μm of ol) complex 3 is added, then vacuumize again and is replaced 3 times with ethylene；The toluene of 500mL is injected,
The toluene solution (toluene solution of 2mmol/L) of four (pentafluorophenyl group) borate of 5mL N, N- dimethyl puratized agricultural spray is added, makes Ni/B
=1,5mL allyltrimethoxysilanis (28.7mmol) keep the ethylene pressure of 10atm, are stirred to react at 70 DEG C
30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, obtains the performance of polymer, polymerization activity and polymer
Parameter is as shown in table 1.
Comparative example 1
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；6.6mg (10 μm of ol) comparative catalyst A (complex A, shown in structure such as formula (IV)) is added, then vacuumizes again simultaneously
It is replaced 3 times with ethylene；The toluene of 500mL is injected, adding 6.5mL methylaluminoxane (MAO), (toluene of 1.53mol/L is molten
Liquid), so that Al/Ni=1000,5mL allyltrimethoxysilanis (28.7mmol) is kept the ethylene pressure of 10atm at 70 DEG C
Power is stirred to react 30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, only seldom weight polymers generate, and gather
The performance parameter for closing activity and polymer is as shown in table 1.
Comparative example 2
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；6.6mg (10 μm of ol) comparative catalyst A (complex A, shown in structure such as formula (IV)) is added, then vacuumizes again simultaneously
It is replaced 3 times with ethylene；The toluene of 500mL is injected, adding 6.5mL methylaluminoxane (MAO), (toluene of 1.53mol/L is molten
Liquid), so that Al/Ni=1000,5mL vinyltrimethoxysilanes (28.7mmol) is kept the ethylene pressure of 10atm at 70 DEG C
Power is stirred to react 30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, is generated without polymer.
Comparative example 3
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；6.3mg (10 μm of ol) comparative catalyst B (complex B, shown in structure such as formula (V)) is added, then vacuumizes again simultaneously
It is replaced 3 times with ethylene；The toluene of 500mL is injected, adding 6.5mL methylaluminoxane (MAO), (toluene of 1.53mol/L is molten
Liquid), so that Al/Ni=1000,5mL allyltrimethoxysilanis (28.7mmol) is kept the ethylene pressure of 10atm at 70 DEG C
Power is stirred to react 30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, is generated without polymer.
Comparative example 4
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times；6.0mg (10 μm of ol) comparative catalyst C is added, (complex C, shown in structure such as formula (VI)) is then vacuumized again
It is used in combination ethylene to replace 3 times；The toluene of 500mL is injected, adding 6.5mL methylaluminoxane (MAO), (toluene of 1.53mol/L is molten
Liquid), so that Al/Ni=1000,5mL allyltrimethoxysilanis (28.7mmol) is kept the ethylene pressure of 10atm at 70 DEG C
Power is stirred to react 30min.It is finally neutralized with the ethanol solution that 5 volume % hydrochloric acid are acidified, is generated without polymer.
Table 1
As can be seen from Table 1, the Copolymerization activity of the carbon monoxide-olefin polymeric in embodiment reaches as high as 12.10 × 106g·
mol-1(Ni)·h-1.Compared to the complex of comparative example 1~4, the complex that embodiment 1~19 uses makes as major catalyst
The Copolymerization activity of used time significantly improves, and the molecular weight of resulting polymers is apparently higher than comparative example resulting polymers, comonomer, first
The content of base also significantly improves, and the molecular weight distribution of polymer is less than comparative example, and the degree of branching and molecular weight of polymer can be
Regulated and controled in wider range.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of illustrated embodiment, for the art
Many modifications and changes will be apparent from for those of ordinary skill.
Claims (10)
1. the copolymerization process of a kind of ethylene and end alkenyl silanes/siloxanes, this method include：In the presence of carbon monoxide-olefin polymeric
Under, so that ethylene is carried out copolymerization with end alkenyl silanes/siloxanes, which is characterized in that the carbon monoxide-olefin polymeric includes master
Catalyst, co-catalyst and optional chain-transferring agent, wherein the major catalyst is selected from complex shown in formula (I) at least
It is a kind of：
In formula (I), R1~R10It is identical or different, it is each independently selected from hydrogen, saturated or unsaturated alkyl, oxyl or halogen
Element；M is selected from VIII race's metal, and X is halogen.
2. copolymerization process according to claim 1, wherein in formula (I), R1~R10It is each independently selected from hydrogen, C1~C10
Saturation or unsaturated alkyl, C1~C10Alkoxy or halogen；
Preferably, R1~R10It is each independently selected from hydrogen, C1~C6Alkyl, C2~C6Alkenyl, C1~C6Alkoxy or halogen
Element；
Preferably, M is nickel.
3. copolymerization process according to claim 1, wherein the major catalyst in following complex at least one
Kind,
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl；
And in complex 1~22, R7~R10It is hydrogen, M is nickel.
4. copolymerization process according to claim 1, wherein the co-catalyst be selected from alkylaluminoxane, aryl boron and
At least one of borate；
It is preferred that the chain-transferring agent is selected from trialkylaluminium and/or dialkyl group zinc.
5. copolymerization process according to claim 4, wherein aluminium rubs with M in the major catalyst in the co-catalyst
You are than being (10~100000) ︰ 1；Or in the co-catalyst in boron and the major catalyst molar ratio of M be (0.01~
1000) 1 ︰.
6. copolymerization process according to claim 4, wherein aluminium rubs with M in the major catalyst in the chain-transferring agent
You are than being (1~10000) ︰ 1；Or the molar ratio of zinc and M in the major catalyst are (1~1000) ︰ 1 in the chain-transferring agent.
7. copolymerization process according to claim 1, wherein end alkenyl silanes are selected from compound shown in formula (II) at least
One kind, end alkenyl siloxane are selected from least one of compound shown in formula (III)：
In formula (II), m, n are respectively 0 or positive integer, respectively preferably 0~20 integer；
In formula (III), p, q are respectively 0 or positive integer, respectively preferably 0~20 integer.
8. copolymerization process according to claim 1, wherein the temperature of the copolyreaction is -20 DEG C to 200 DEG C, preferably
It is 40~120 DEG C, more preferably 60~110 DEG C；
The pressure of ethylene is 1~1000atm, preferably 1~200atm.
9. according to the copolymerization process described in claim 1,7 or 8, wherein the dosage of the end alkenyl silanes/siloxanes is 0.01
~3000mmol/L, preferably 0.1~1000mmol/L.
10. copolymerization process according to claim 1, wherein the dosage of the major catalyst is 0.00001~100mmol/
L, preferably 0.001~1mmol/L.
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