CN106565871B - The preparation method of catalyst component for olefin and preparation method thereof and polyethylene - Google Patents
The preparation method of catalyst component for olefin and preparation method thereof and polyethylene Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst component for olefin, which contains carrier, titanium-containing compound and 1, bis- ethers electron donor of 3-, and 1,3-, the bis- ethers electron donor is formula (1) structure compound represented.The preparation method of polyethylene the present invention also provides the preparation method of above-mentioned catalyst component for olefin and using above-mentioned catalytic component.The novel catalyst component for olefin provided by the invention, it is cheap and easily-available, it can reduce production cost.When being used for catalyzed ethylene polymerization, catalytic activity with higher can obtain fusing point and polyethylene product that crystallinity is met the requirements
Description
Technical field
The present invention relates to the preparation methods of catalyst component for olefin and preparation method thereof and polyethylene.
Background technique
Polyolefin resin directly influences development and its people's consumption water of national economy as important one of synthetic material
Flat raising is especially closely related with downstream industries such as packaging, agricultural, building, automobile, Electrical and Electronics.The coordination of alkene
Polymerization is that the catalyst system formed using transistion metal compound and organo-metallic compound is carried out.In the early 1950s,
The frontier of Polymer Synthesizing has been opened up in the appearance of Ziegler-Natta catalyst system and coordination polymerization, promotes ethylene low pressure
The foundation and development of polymerization and the industry of propylene stereospecfic polymerization.Since the 1960s, successively to have multidigit to be engaged in metal organic
The expert of olefin polymerization catalysis research obtains Nobel chemistry Prize.
So far, the solid titanium catalyst component using magnesium, titanium, chlorine and electron donor as basis is current poly- second
The catalyst that alkene industry is widely used, wherein electron donor compound makes one of indispensable ingredient in catalyst, and with
The development of electron donor compound also result in the continuous developments of polyethylene catalysts.Currently, existing a large amount of interior electron
Body compound is well-known, for example, monoesters class, two esters, ethers, two ethers, amine, alcohol etc. and its derivative, wherein more
Commonly aromatic diesters class compound, such as phthalic acid ester di-n-butyl or diisobutyl phthalate etc. (referring to
CN1580034A (2005), CN1690090A (2005) etc.).
Two ethers electron donors, especially 1,3- diether are a kind of emerging electron donors, and the research to two ethers is to work as
One hot spot of preceding research.The application of current two ethers electron donor is mainly applied in the polymerization of propylene, but it is answered
Polymerization studies for ethylene are less, and it is existing include 1,3- diether solid titanium catalyst component all have it is higher at
This.
Summary of the invention
The purpose of the present invention is to provide a kind of novel catalyst component for olefin and preparation method thereof, and adopt
The method for preparing polyethylene with the novel catalyst component for olefin.
For this purpose, the present invention provides a kind of catalyst component for olefin, which contains carrier, titaniferous chemical combination
Object and 1, bis- ethers electron donor of 3-, wherein 1,3-, the bis- ethers electron donor is formula (1) structure compound represented:
Formula (1)
Wherein, R1、R2、R3And R4Be each independently selected from hydrogen, the linear or branched alkyl group of C1-C20, C2-C10 alkenyl,
Unsubstituted or the C3-C10 that is replaced by the alkyl single-point or multiple spot of C1-C4 naphthenic base, unsubstituted or by C1-C4 alkane
The alkyl and alkyl list unsubstituted or by C1-C4 of base single-point or the multiple spot phenyl replaced, the C1-C4 being substituted by phenyl
The naphthalene that point or multiple spot replace, also, R3And R4It is not hydrogen.
The present invention also provides the preparation methods of above-mentioned catalyst component for olefin, wherein this method comprises: by institute
Carrier, titanium-containing compound and bis- ethers electron donor of 1,3- is stated to be heated and contacted.
The present invention also provides a kind of preparation methods of polyethylene, this method comprises: in above-mentioned catalytic component, You Jirong
In the presence of agent and triethyl aluminum, ethylene is subjected to polymerization reaction.
The novel catalyst component for olefin provided by the invention, it is cheap and easily-available, it can reduce production cost；And
And when being used for catalyzed ethylene polymerization, catalytic activity with higher can obtain fusing point and poly- second that crystallinity is met the requirements
Alkene product, especially fusing point are the polyethylene product of 133.9-137.5 DEG C of range and crystallinity within the scope of 30-75.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments 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 a kind of catalyst component for olefin, the catalytic component contain carrier, titanium-containing compound and
1,3- bis- ethers electron donor, wherein 1,3-, the bis- ethers electron donor is formula (1) structure compound represented:
Formula (1)
Wherein, R1、R2、R3And R4Be each independently selected from hydrogen, the linear or branched alkyl group of C1-C20, C2-C10 alkenyl,
Unsubstituted or the C3-C10 that is replaced by the alkyl single-point or multiple spot of C1-C4 naphthenic base, unsubstituted or by C1-C4 alkane
The alkyl and alkyl list unsubstituted or by C1-C4 of base single-point or the multiple spot phenyl replaced, the C1-C4 being substituted by phenyl
The naphthalene that point or multiple spot replace, also, R3And R4It is not hydrogen.
The present invention is using above-mentioned formula (1) structure compound represented as the institute in the catalyst component for olefin
1,3-, bis- ethers electron donor is stated, formula (1) structure compound represented is connected with electron on the phenyl ring with rigid structure
The flexible structure of the strong alkoxy of ability and the weaker phenol oxide structure of electron donation, such design, which can help, preferably to help
Catalysis in olefine polymerization especially vinyl polymerization.
According to the present invention, excellent in order to obtain the catalytic component that can be conducive to catalysis in olefine polymerization especially vinyl polymerization
Selection of land, in formula (1), R1、R2、R3And R4It is each independently selected from the alkene of hydrogen, the linear or branched alkyl group of C1-C10, C2-C8
It is base, unsubstituted or the C5-C10 that is replaced by the alkyl single-point or multiple spot of C1-C4 naphthenic base, unsubstituted or by C1-C4
Alkyl single-point or multiple spot replace phenyl and the C1-C4 being substituted by phenyl alkyl.It is highly preferred that R1、R2、R3And R4Respectively
From the linear or branched alkyl group, unsubstituted or replaced by the alkyl single-point or multiple spot of C1-C4 independently selected from hydrogen, C1-C8
It is the naphthenic base of C5-C8, unsubstituted or by phenyl that the alkyl single-point or multiple spot of C1-C4 replace and be substituted by phenyl
The alkyl of C1-C4.It is further preferred that R1、R2、R3And R4Be each independently selected from hydrogen, C1-C6 linear or branched alkyl group,
Unsubstituted or the C5-C6 that is replaced by the alkyl single-point or multiple spot of C1-C4 naphthenic base, unsubstituted or by C1-C4 alkane
The alkyl of phenyl and the C1-C4 being substituted by phenyl that base single-point or multiple spot replace.It is further preferred that R1、R2、R3And R4
It is each independently selected from linear or branched alkyl group (such as methyl, ethyl, propyl, isopropyl, normal-butyl, the isobutyl of hydrogen, C1-C4
Base, tert-butyl), cyclohexyl, phenyl and benzyl.
In a kind of particularly preferred embodiment of the invention, in formula (1), R2It is not hydrogen.
In another particularly preferred embodiment of the invention, in formula (1), R1And R2It is each independently selected from hydrogen, first
Base (Me), ethyl (Et), propyl (Pr), isopropyl (i-Pr), normal-butyl (Bu), isobutyl group (i-Bu) or tert-butyl (t-Bu),
And R2It is not hydrogen, R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl or cyclohexyl, R4Selected from second
Base, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl or phenyl.
According to the present invention, above-mentioned 1,3-, bis- ethers electron donor can be commercially available product, can also be conventional according to this field
Method preparation, it is preferable that the preparation method of 1,3-, the bis- ethers electron donor includes:
NaH will be added and stirred after a certain period of time at (20-30 DEG C) of room temperature in the THF solution of corresponding alkoxy benzylalcohol,
Halogenated alkane is added into gained mixture, is heated to reflux, deionized water is then added, and be extracted with ethyl acetate, is associated with
Machine phase.Target product is obtained through column chromatography for separation.Wherein, the molar ratio of alkoxy benzylalcohol and NaH can be 1:1-1.5, alcoxyl
The molar ratio of base benzylalcohol and halogenated alkane can be 1:1-1.2.The condition of the reflux may include: that temperature is 65-66 DEG C, when
Between be 15-20h.
According to the present invention, the carrier is not particularly limited, can is the carrier material of this field routine, preferably
Ground, the carrier are by formula MgYyR2-y·nR5OH·mBX3The carrier of expression is one or more, also, Y is halogen；R is C1-
The alkyl of C4 or the alkoxy of C1-C4；R5For the alkyl of C1-C4；X is halogen；N is 1-6, and m 0.1-0.35, y are 1 or 2.Its
In, y is preferably 2；Y is preferably chlorine；R5For normal-butyl (Bu), n-propyl (Pr) or ethyl (Et)；X is preferably chlorine.In the present invention
A kind of preferred embodiment in, it is above-mentioned by formula MgYyR2-y·nR5OH·mBX3The carrier of expression is MgCl2·nBuOH·
mBCl3、MgCl2·nPrOH·mBCl3Or MgCl2·nEtOH·mBCl3。
The carrier can be commercially available product, can also be made by the method for this field routine, be MgCl with carrier2·
nR5OH·mBCl3Preparation for, the preparation method of the carrier includes: under the conditions of anhydrous and oxygen-free, by MgCl2And BCl3Having
It is mixed in solvent, R is then added5OH, temperature rising reflux filter, dry cake after cooling.Wherein, MgCl2And BCl3Mole
Amount ratio is preferably 1-10:1 (preferably 3-9:1)；MgCl2And R5The mole dosage of OH is than being preferably 1:2-5.The organic solvent
It such as can be one of normal heptane, n-hexane, petroleum ether and hydrogasoline or a variety of.The condition of the reflux is preferably wrapped
Include: temperature is 110-130 DEG C, time 6-10h.
According to the present invention, the titanium-containing compound is not particularly limited, can be used for using this field is conventional
The titanium-containing compound of catalysis in olefine polymerization, it is preferable that the titanium-containing compound is by formula TiX 'x(OR6)4-xIt indicates, wherein X ' is halogen
Element, x are the integer of 1-4, R6For the alkyl of C1-C5.It is highly preferred that the titanium-containing compound is TiCl4。
In a kind of particularly preferred embodiment of the invention, in formula (1), R1And R2It is each independently selected from hydrogen, first
Base, ethyl, propyl, isopropyl, normal-butyl, isobutyl group or tert-butyl, and R2It is not hydrogen, R3Selected from methyl, ethyl, propyl, isopropyl
Base, normal-butyl, isobutyl group, tert-butyl or cyclohexyl, R4Selected from ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl,
Cyclohexyl or phenyl；The carrier is MgCl2·nBuOH·mBCl3、MgCl2·nPrOH·mBCl3Or MgCl2·nEtOH·
mBCl3, n 1-6, m 0.1-0.35；The titanium-containing compound is TiCl4。
According to the present invention, in order to obtaining the more superior catalyst component for olefin of performance, it is preferable that described
The molar ratio of bis- ethers electron donor of titanium-containing compound and 1, the 3- is 3-10:1, more preferably 5-7:1.
According to the present invention, when using above-mentioned by formula MgYyR2-y·nR5OH·mBX3Described in the one or more conducts indicated
When carrier, the molar ratio of bis- ethers electron donor of magnesium elements and 1, the 3- is 10-40:1, more preferably 15- in the carrier
30:1.
In a kind of particularly preferred embodiment of the invention, in the formula (1) that 1,3-, the bis- ethers electron donor is,
R1And R2It is each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group or tert-butyl, and R2It is not hydrogen,
R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl or cyclohexyl, R4Selected from ethyl, propyl, isopropyl
Base, normal-butyl, isobutyl group, tert-butyl, cyclohexyl or phenyl；The carrier is MgCl2·nBuOH·mBCl3、MgCl2·
nPrOH·mBCl3Or MgCl2·nEtOH·mBCl3, n 1-6, m 0.1-0.35；The titanium-containing compound is TiCl4；And
And the carrier, TiCl in terms of magnesium elements4Molar ratio with 1,3-, the bis- ethers electron donor is 3-10:10-40:1,
More preferably 5-7:15-30:1.
In terms of the invention, it is understood that " catalytic component contains carrier, titanium-containing compound and 1,3- diether
Class electron donor " means that the catalyst can be by carrier, titanium-containing compound and 1, bis- ethers electron donor of 3- composition, yet
It may include other additives, it is understood that the active constituent for being the catalytic component is the carrier, titaniferous chemical combination
The combination of bis- ethers electron donor of object and 1,3-.
The present invention also provides the preparation methods of above-mentioned catalyst component for olefin, this method comprises: by the load
Body, titanium-containing compound and bis- ethers electron donor of 1,3- are heated and are contacted.
Wherein, the carrier, titanium-containing compound and 1, bis- ethers electron donor of 3- be it is noted hereinabove, it is no longer superfluous here
It states.
According to the present invention, the dosage of the carrier can be carried out according to the composition of required catalyst component for olefin
It determines, it is preferable that when the carrier is by formula MgYyR2-y·nR5OH·mBX3The carrier and institute when expression, in terms of magnesium elements
The mole dosage ratio for stating 1,3-, bis- ethers electron donor is 5-15:1, more preferably 8-13:1.
According to the present invention, the dosage of the titanium-containing compound can be according to the group of required catalyst component for olefin
At being determined, it is preferable that the mole dosage ratio of bis- ethers electron donor of the titanium-containing compound and 1, the 3- is 150-
250:1, more preferably 170-230:1.
According to the present invention, the carrier, titanium-containing compound and 1, bis- ethers electron donor of 3- is in the also contacts process
In, it is loaded and complexation reaction, to obtain the catalyst component for olefin that there is electron donor to be coordinated.Therefore,
There is no particular limitation to the condition for heating and contacting by the present invention, as long as olefin polymerization catalysis of the invention can be obtained
Agent component, in order to obtain more superior catalyst component for olefin, under preferable case, the condition packet of the contact
Include: temperature is 110-130 DEG C, time 1-3h.
According to the present invention, in order to the catalyst component for olefin is extracted from the reaction product after contact
Come, after the present invention can also be included in the contact, filter reaction product, obtained sediment with organic solvent (such as
One of normal heptane, n-hexane, petroleum ether and hydrogasoline are a variety of) washing, be then dried again (such as under vacuum
Dry 5-8h at 60-80 DEG C), dry catalyst fines are obtained with this.
The present invention also provides a kind of preparation methods of polyethylene, this method comprises: in above-mentioned catalytic component, You Jirong
In the presence of agent and triethyl aluminum, ethylene is subjected to polymerization reaction.
According to the present invention, the catalytic component is defined above, and details are not described herein.
According to the present invention, in the polymerization reaction of the ethylene, the dosage of the catalytic component is not particularly limited,
It can change in a wider scope, it is preferable that the dosage of the catalytic component makes the catalyst in terms of titanium elements
Component and the molar ratio of the triethyl aluminum in terms of aluminium element are 1:20-100, preferably 1:40-50.
According to the present invention, catalytic component of the invention and triethyl aluminum cooperation can be shown higher in vinyl polymerization
Catalytic activity, the catalytic activity that can be shown be 1400-2600gPE/gTihatm.
In the case of, according to the invention it is preferred to, the temperature of the polymerization reaction is 15-100 DEG C.The time of the polymerization reaction
It can be adjusted by the additional amount of ethylene, there is no particular limitation to this by the present invention.
According to the present invention, the polymerization reaction of the ethylene carries out in the presence of an organic, and the organic solvent for example may be used
Think one of normal heptane, n-hexane, petroleum ether and hydrogasoline or a variety of.The polymerization reaction is particularly preferably by the way of
Are as follows: first the catalytic component, triethyl aluminum and solvent are mixed, the mode of ethylene gas is then passed through into the mixed liquor.
The dosage of the solvent is not particularly limited, can be selected according to the dosage of the conventional solvent of this field, example
Such as relative to the catalytic component of 1mg, the dosage of the solvent is 1-5mL.
According to the present invention, the preparation method of above-mentioned polyethylene, since catalytic component and triethyl aluminum of the invention can
Preferably cooperation is catalyzed, and polyethylene is preferably polymerize, particularly preferably, above-mentioned polyethylene of the invention
Preparation method the polyethylene product that fusing point (Tm) is 133.9-137.5 DEG C, crystallinity (Xc) is 30-75 can be made.
The present invention will be described in detail by way of examples below.
In following example,
Carrier MgCl2·nBuOH·mBCl3In n and m be to be measured by the increase and decrease and complexometric titration method of weight；
The fusing point and crystallinity of polyethylene are measured by differential scanning calorimeter (DSC)；
1H NMR and13C NMR is by the Nuclear Magnetic Resonance of German III 500HD model of Bruker company AVANCE
It measures.
Preparation example 1
Under conditions of anhydrous and oxygen-free, by MgCl2The BCl of (2g, 0.021mol), 7mL3(0.82g, 0.007mol) and
50mL normal heptane is uniformly mixed, and the n-butanol (0.063mol) of 5.8mL is added, and flow back 10h at 120 DEG C, filters pressing after cooling, will
Filter cake is dried under vacuum, and obtaining carrier A1 is MgCl2·nBuOH·mBCl3, n 3, m 1/3.
Preparation example 2
According to method described in preparation example 1, the difference is that using the BCl of 3.5mL3(0.41g, 0.0035mol), obtains
It is MgCl to carrier A22·nBuOH·mBCl3, n 3, m 1/6.
Preparation example 3
According to method described in preparation example 1, the difference is that using the BCl of 2.3mL3(0.27g, 0.0023mol), obtains
It is MgCl to carrier A32·nBuOH·mBCl3, n 3, m 1/9.
Preparation example 4
According to method described in preparation example 2, the difference is that obtaining carrier using the n-butanol (0.105mol) of 9.6mL
A4 is MgCl2·nBuOH·mBCl3, n 5, m 1/6.
Preparation example 5
According to method described in preparation example 2, the difference is that the normal propyl alcohol (0.063mol) using 4.7mL substitutes positive fourth
Alcohol, obtaining carrier A5 is MgCl2·nPrOH·mBCl3, n 3, m 1/6.
Preparation example 6
According to method described in preparation example 2, the difference is that the ethyl alcohol (0.062mol) using 3.6mL substitutes n-butanol,
Obtaining carrier A6 is MgCl2·nEtOH·mBCl3, n 3, m 1/6.
Preparation example 7
NaH is added portionwise in THF (30mL) solution of 5- tert-butyl -2- methoxy benzyl alcohol (2.0g, 10mmol)
(60%, 0.5g, 12.5mmol), (about 25 DEG C) stirring 1h of room temperature are added bromoethane (2.5mL, 25mmol), flow back at 65 DEG C
18h.20mL deionized water is added into gained mixture, ethyl acetate extracts (3 × 15mL), saturated common salt water washing (3 ×
15mL), anhydrous MgSO4It is dry, crude product is obtained after removing solvent.Using silicagel column column chromatography separating-purifying, obtain yellowish
Color liquid (2.01g, 90%).
To obtain R1=H, R2=tert-butyl, R3=methyl, R4Formula (1) structure compound represented of=ethyl, i.e. 4-
Tert-butyl -2- ethoxyl methyl methyl phenyl ethers anisole, hydrogen spectrum, carbon modal data are as follows:1H NMR(500MHz,CDCl3):δ7.41(d,1H),
7.24(dd,1H),6.77(d,1H),4.54(s,2H),3.77(s,3H),3.57(q,2H),1.30(s,9H),1.26(t,
5H)；13C NMR(126MHz,CDCl3):δ154.99,142.99,126.22,126.04,125.03,109.79,77.41,
77.16,76.91,67.67,65.89,55.36,34.09,31.58,15.34.
Preparation example 8
According to method described in preparation example 7, the difference is that bromoethane is replaced with into bromobutane,
To obtain R1=H, R2=tert-butyl, R3=methyl, R4Formula (1) structure compound represented of=normal-butyl, i.e.,
4- tert-butyl -2- butoxymethyl methyl phenyl ethers anisole, hydrogen spectrum, carbon modal data are as follows:1H NMR(500MHz,CDCl3):δ7.42(d,
1H),7.24(dd,1H),6.77(d,1H),4.54(s,2H),3.77(s,3H),3.51(t,2H),1.68–1.58(m,2H),
1.48–1.36(m,2H),1.30(s,10H),0.93(t,3H)；13C NMR(126MHz,CDCl3):δ154.97,143.02,
126.40,125.90,124.93,109.76,77.41,77.16,76.91,70.44,67.81,55.37,34.13,31.98,
31.61,19.53,14.04.
Preparation example 9
According to method described in preparation example 7, the difference is that 5- tert-butyl -2- methoxy benzyl alcohol is replaced with 3,5-
Di-t-butyl -2- methoxy benzyl alcohol,
To obtain R1=tert-butyl, R2=tert-butyl, R3=methyl, R4Chemical combination shown in formula (1) structure of=ethyl
Object, i.e. 2,4- di-t-butyl -6- ethoxymethyl methyl phenyl ethers anisole, hydrogen spectrum, carbon modal data are as follows:1H NMR(500MHz,CDCl3):δ
7.29(dd,1H),4.53(s,1H),3.80(s,2H),3.59(q,1H),1.39(s,5H),1.31(s,5H),1.26(t,
2H)；13C NMR(126MHz,CDCl3):δ155.96,145.64,141.69,130.92,125.55,123.95,77.41,
77.16,76.91,68.46,66.11,62.60,35.39,34.60,31.65,31.20,15.42.
Preparation example 10
According to method described in preparation example 8, the difference is that 5- tert-butyl -2- methoxy benzyl alcohol is replaced with 5- second
Base -3- tert-butyl -2- ethoxybenzene methanol,
To obtain R1=tert-butyl, R2=ethyl, R3=ethyl, R4Chemical combination shown in formula (1) structure of=normal-butyl
Object, i.e. 4- ethyl -6- tert-butyl -2- butoxymethyl phenetole, hydrogen spectrum, carbon modal data are as follows:1H NMR(500MHz,
CDCl3):δ7.23(s,1H),7.03(s,1H),4.80(s,2H),4.07(q,2H),3.35(t,2H),2.72(q,2H),
1.50(m,2H),1.46(s,2H),1.40(t,9H),1.34(t,3H),1.18(t,3H),0.96(t,3H)；13C NMR
(126MHz,CDCl3):δ146.1,138.0,132.4,125.5,125.3,123.1,70.4,69.7,69.6,35.0,32.2,
31.6,31.6,31.6,28.8,19.0,14.8,14.5,14.1.
Preparation example 11
According to method described in preparation example 7, the difference is that 5- tert-butyl -2- methoxy benzyl alcohol is replaced with 3,5-
Di-t-butyl -2- cyclohexyloxy benzyl alcohol；Original bromoethane is become into bromocyclohexane,
To obtain R1=tert-butyl, R2=tert-butyl, R3=cyclohexyl, R4Change shown in formula (1) structure of=cyclohexyl
Close object, i.e. 4,6- di-t-butyl -2- hexamethylene oxygen methylphenyl cyclohexyl ether, hydrogen spectrum, carbon modal data are as follows:1H NMR
(500MHz,CDCl3):δ7.45(s,1H),7.14(s,1H),4.8(s,2H),3.64(m,1H),3.24(m,1H),1.95-
1.70(m,4H),1.70-1.45(m,4H),1.53-1.43(m,8H),1.46-1.44(m,4H),1.40(s,9H),1.31(s,
9H)；13C NMR(126MHz,CDCl3):δ145.8,141.1,132.1,124.3,122.8,122.8,85.6,78.6,67.4,
35.0,34.8,33.9,33.9,32.4,32.4,31.6,31.6,31.6,31.3,31.3,31.3,26.0,26.0,26.0,
24.2,24.2,24.2,24.2.
Embodiment 1
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A1 (mole of magnesium elements is 8.5mmol), 15mL4(26g, 0.137mol) and the tertiary fourth of 4-
Base -2- ethoxyl methyl methyl phenyl ethers anisole (0.16g, 0.72mmol) is added in Schlenk reactor, is heated 2h at 120 DEG C, is added
After heat, filter cake is washed three times with normal heptane, is dried to obtain 1.05g catalyst fines CA1 by filtering.
Embodiment 2
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
According to method described in embodiment 1, the difference is that use 1g carrier A2 (mole of magnesium elements for
Carrier A1 8.8mmol) is replaced, to obtain 0.89g catalyst fines CA2.
Embodiment 3
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
According to method described in embodiment 1, the difference is that use 1g carrier A3 (mole of magnesium elements for
Carrier A1 8.3mmol) is replaced, to obtain 0.93g catalyst fines CA3.
Embodiment 4
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
According to method described in embodiment 1, the difference is that use 1g carrier A4 (mole of magnesium elements for
Carrier A1 8.7mmol) is replaced, to obtain 1.07g catalyst fines CA4.
Embodiment 5
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
According to method described in embodiment 1, the difference is that use 1g carrier A5 (mole of magnesium elements for
Carrier A1 7.9mmol) is replaced, to obtain 1.06g catalyst fines CA5.
Embodiment 6
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A5 (mole of magnesium elements is 7.4mmol), 15mL4(26g, 0.137mol) and the tertiary fourth of 4-
Base -2- butoxymethyl methyl phenyl ethers anisole (0.17g, 0.68mmol) is added in Schlenk reactor, 1h is heated at 130 DEG C, so
After filter, filter cake is washed three times with normal heptane, is dried to obtain 0.97g catalyst fines CA6.
Embodiment 7
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A6 (mole in terms of magnesium elements is 7.2mmol), 15mL4(26g, 0.137mol) and 4-
Tert-butyl -2- Phenoxymethyl methyl phenyl ethers anisole (0.18g, 0.66mmol) is added in Schlenk reactor, is heated at 110 DEG C
Then 2.5h is filtered, filter cake is washed three times with normal heptane, is dried to obtain 1.1g catalyst fines CA7.
Embodiment 8
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A6 (mole in terms of magnesium elements is 7.2mmol), 15mL4(26g, 0.137mol) and 4-
Ethyl -6- tert-butyl -2- butoxymethyl phenetole (0.21g, 0.72mmol) is added in Schlenk reactor, at 125 DEG C
Lower heating 2h, is then filtered, and filter cake is washed three times with normal heptane, is dried to obtain 1.03g catalyst fines CA8.
Embodiment 9
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A6 (mole in terms of magnesium elements is 7.2mmol), 1mL4(26g, 0.137mol) and 4,
6- di-t-butyl -2- hexamethylene oxygen methylphenyl cyclohexyl ether (0.25g, 0.62mmol) is added in Schlenk reactor,
2h is heated at 120 DEG C, is then filtered, and filter cake is washed three times with normal heptane, is dried to obtain 0.91g catalyst fines CA9.
Embodiment 10
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A6 (mole in terms of magnesium elements is 7.2mmol), 15mL4(26g, 0.137mol) and 4-
Tert-butyl -6- isopropyl -2- phenoxymethyl propyloxy phenyl base ether (0.26g, 0.76mmol) is added to Schlenk reactor
In, 2h is heated at 120 DEG C, is then filtered, and filter cake is washed three times with normal heptane, is dried to obtain 0.97g catalyst fines
CA10。
Embodiment 11
The present embodiment is for illustrating catalyst component for olefin and preparation method thereof.
By the TiCl of 1g carrier A6 (mole in terms of magnesium elements is 7.2mmolmol), 15mL4(26g, 0.137mol)
It is anti-that Schlenk is added to 4- isopropyl -6- tert-butyl -2- t-butoxymethyl phenylcyclohexyl ether (0.25g, 0.69mmol)
It answers in device, 2h is heated at 120 DEG C, is then filtered, filter cake is washed three times with normal heptane, is dried to obtain 1.04g catalyst powder
Last CA11.
Embodiment 12
According to method described in embodiment 1, the difference is that carrier is using undoped modified δ-MgCl2It (is purchased from
Aladdin company α-MgCl2It is changed into δ-MgCl by chemical precipitation method2), it is dried to obtain 1.02g catalyst fines CA12.
It polymerize test case 1
In ampere bottle, the catalyst (catalyst type be shown in Table 1) of 10mg, the normal heptane and AlEt of 15mL will be added3
(so that the molar ratio of aluminium and Ti are 50:1), under the conditions of 1atm, is bubbled into ethylene with the speed of 1 bubbles per second, at 20 DEG C
Lower polymerization 1h, stopping are passed through ethylene, and hydrochloric acid/alcohol mixeding liquid is added and terminates reaction, and polymerizate washs 3 times through dehydrated alcohol,
Drying weighing, and measure fusing point and crystallinity.
Table 1
Can be seen that catalytic component and triethyl aluminum of the invention by the data of table 1 can preferably cooperate progress
Catalysis, enables polyethylene preferably to be polymerize, particularly preferably, the preparation method of above-mentioned polyethylene of the invention can
It is 133.9-137.5 DEG C of (preferably 135.1-136.5 DEG C), crystallinity (X that fusing point (Tm), which is made,c) be 30-75 (preferably
Polyethylene product 42.6-60.7).Using by formula MgYyR2-y·nR5OH·mBX3The carrier of expression and formula of the invention (1) knot
Structure compound represented as the bis- ethers electron donor of 1,3- in the case where (such as embodiment 1 and embodiment 12 are opposite
Than), more superior catalytic effect can be obtained.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (25)
1. a kind of catalyst component for olefin, which contains carrier, titanium-containing compound and 1, and bis- ethers of 3- is given
Electron, which is characterized in that 1,3-, the bis- ethers electron donor is formula (1) structure compound represented:
Formula (1)
Wherein, R1、R2、R3And R4It is each independently selected from hydrogen, the linear or branched alkyl group of C1-C20, the alkenyl of C2-C10, do not take
The naphthenic base of C3-C10 that is generation or being replaced by the alkyl single-point or multiple spot of C1-C4, unsubstituted or by C1-C4 alkyl list
Point or the multiple spot phenyl replaced, the C1-C4 being substituted by phenyl alkyl and it is unsubstituted or by the alkyl single-point of C1-C4 or
The naphthalene that multiple spot replaces, also, R3And R4It is not hydrogen.
2. catalyst component for olefin according to claim 1, wherein in formula (1), R1、R2、R3And R4It is respectively independent
Ground is selected from hydrogen, the linear or branched alkyl group of C1-C10, the alkenyl of C2-C8, unsubstituted or by C1-C4 alkyl single-point or multiple spot
The naphthenic base of substituted C5-C10, the unsubstituted or phenyl that is replaced by the alkyl single-point or multiple spot of C1-C4 and by phenyl
The alkyl of substituted C1-C4.
3. catalyst component for olefin according to claim 2, wherein R1、R2、R3And R4It is each independently selected from
Hydrogen, the linear or branched alkyl group of C1-C8, the unsubstituted or cycloalkanes of C5-C8 that is replaced by the alkyl single-point or multiple spot of C1-C4
Base, the unsubstituted or alkyl of phenyl and the C1-C4 being substituted by phenyl that is replaced by the alkyl single-point or multiple spot of C1-C4.
4. catalyst component for olefin according to claim 3, wherein R1、R2、R3And R4It is each independently selected from
Hydrogen, the linear or branched alkyl group of C1-C6, the unsubstituted or cycloalkanes of C5-C6 that is replaced by the alkyl single-point or multiple spot of C1-C4
Base, the unsubstituted or alkyl of phenyl and the C1-C4 being substituted by phenyl that is replaced by the alkyl single-point or multiple spot of C1-C4.
5. catalyst component for olefin according to claim 4, wherein R1、R2、R3And R4It is each independently selected from
Hydrogen, the linear or branched alkyl group of C1-C4, cyclohexyl, phenyl and benzyl.
6. catalyst component for olefin according to claim 1, wherein in formula (1), R2It is not hydrogen.
7. catalyst component for olefin according to claim 1, wherein the carrier is by formula MgYyR2-y·
nR5OH·mBX3The carrier of expression is one or more, also, Y is halogen；R is the alkyl of C1-C4 or the alkoxy of C1-C4；R5
For the alkyl of C1-C4；X is halogen；N is 1-6, and m 0.1-0.35, y are 1 or 2.
8. catalyst component for olefin according to claim 7, wherein y 2.
9. catalyst component for olefin according to claim 7, wherein Y is chlorine.
10. catalyst component for olefin according to claim 7, wherein R5For normal-butyl, n-propyl or ethyl.
11. catalyst component for olefin according to claim 7, wherein X is chlorine.
12. catalyst component for olefin according to claim 1, wherein the titanium-containing compound and described 1,3-
The molar ratio of two ethers electron donors is 3-10:1.
13. catalyst component for olefin according to claim 12, wherein the titanium-containing compound and described 1,3-
The molar ratio of two ethers electron donors is 5-7:1.
14. according to claim 1 or catalyst component for olefin described in 13, wherein the titanium-containing compound is by formula
TiX’x(OR6)4-xIt indicates, wherein X ' is halogen, and x is the integer of 1-4, R6For the alkyl of C1-C5.
15. catalyst component for olefin according to claim 14, wherein the titanium-containing compound is TiCl4。
16. catalyst component for olefin according to claim 1, wherein magnesium elements and described 1 in the carrier,
The molar ratio of bis- ethers electron donor of 3- is 10-40:1.
17. catalyst component for olefin according to claim 16, wherein magnesium elements and described 1 in the carrier,
The molar ratio of bis- ethers electron donor of 3- is 15-30:1.
18. the preparation method of catalyst component for olefin described in a kind of any one of claim 1-17, this method
It include: that the carrier, titanium-containing compound and bis- ethers electron donor of 1,3- are heated and contacted.
19. according to the method for claim 18, wherein bis- ethers electron donor of the titanium-containing compound and 1, the 3-
Mole dosage ratio is 150-250:1.
20. according to the method for claim 19, wherein bis- ethers electron donor of the titanium-containing compound and 1, the 3-
Mole dosage ratio is 170-230:1.
21. according to the method for claim 18, wherein when the carrier is by formula MgYyR2-y·nR5OH·mBX3When expression,
The mole dosage ratio of bis- ethers electron donor of the carrier and the 1,3- in terms of magnesium elements is 5-15:1.
22. according to the method for claim 21, wherein the carrier and 1, the 3-, bis- ethers in terms of magnesium elements are to electricity
The mole dosage ratio of daughter is 8-13:1.
23. according to the method for claim 18, wherein the condition of the contact includes: that temperature is 110-130 DEG C, the time
For 1-3h.
24. a kind of preparation method of polyethylene, which is characterized in that this method comprises: in any one of claim 1-17 institute
In the presence of catalytic component, organic solvent and the triethyl aluminum stated, ethylene is subjected to polymerization reaction.
25. the preparation method of polyethylene according to claim 24, wherein the dosage of the catalytic component makes with titanium
The catalytic component of element meter and the molar ratio of the triethyl aluminum in terms of aluminium element are 1:20-100.
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