CN100390207C - Process for preparing polyolefin composite materials - Google Patents
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- CN100390207C CN100390207C CNB2004100385123A CN200410038512A CN100390207C CN 100390207 C CN100390207 C CN 100390207C CN B2004100385123 A CNB2004100385123 A CN B2004100385123A CN 200410038512 A CN200410038512 A CN 200410038512A CN 100390207 C CN100390207 C CN 100390207C
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Abstract
The present invention relates to a method for preparing a polyolefin composite material, which comprises the main steps that (1) the polyreaction of propene and a monomer containing boron is carried out by a loading type titanium tetrachloride catalyst; (2) afterwards, an obtained polymer is oxidized and hydrolyzed so that a polypropylene copolymer containing a fixed quantity of hydroxyl radical is obtained; (3) then, a metallocene catalyst is loaded to polypropylene containing the hydroxyl radical; (4) finally, other alkene is polymerized in the obtained polypropylene so as to form the polyolefin composite material, wherein the rate of the polypropylene to other olefin polymers can be conveniently regulated so that the performance of the final material can be regulated.
Description
Technical field
The present invention relates to a kind of preparation method of composite polyolefine material.
Background technology
Different polymer materials mixed forming polymer composites (claiming polymer alloy again), can make material obtain the advantage of two or more polymkeric substance simultaneously, can improve every performance of material effectively.At present, the method for formation polymer alloy mainly contains two kinds.A kind of is the method for traditional mechanical blending, and another kind is an original position synthetic method.The method of mechanical blending is difficult to make the polymkeric substance thorough mixing, particularly to nonpolar polyolefine material, is difficult to mix, and nonpolar polyolefine material is mixed with the polar polymer materials.The method of the synthetic alloy of original position is at a kind of surface of polymkeric substance or inner directly synthetic another kind or several polymkeric substance, thereby realizes the in-situ blending of different polymkeric substance.Because second kind of polymkeric substance is in the inside of first kind of polymkeric substance, not only can obtain very homogeneous polymer matrix material, and can make the polymkeric substance that did not mix originally realize uniform mixing, this is that mechanical blending can't be accomplished at all.Owing to have good performance, is the research of representative this aspect very active with particle synthetic technology (RGT) at present by the material of in-situ blending method preparation.
The Spheripol technology is one of industrialized the earliest RGT technology.This technology be polypropylene after the first step mass polymerization, enter the still activated catalyzer of gas phase utilization and carry out second third copolymerization.Thereby obtain the polyolefine material of high impact properties.Spherilene is similar to the Spheripol technology, mainly is the technological process that is used for producing the ethene alloy.In the Interloy process, at first using Ziegler-Natta catalyst to synthesize polyolefin particles, in this particle, carry out free radical catalysis graft copolymerization with radioactive source then, mainly is the polymkeric substance that forms polar monomer in particle.The Hivalloy technology is behind Ziegler-Natta catalyzed polymerization alkene, use superoxide in the polyolefine space that forms, to carry out grafting radical polymerization with parent, it can make polar monomer even the graft polymerization in polyolefin substrate of non-olefinic monomer, can make widely that comonomer reacts, as vinylbenzene, propylene cyanogen, CALCIUM ACRYLATE etc.; Thereby make polyolefine material have the high-performance of engineering plastics.The Cataloy technology has farthest been utilized the superiority of RGT, the advantage that this technology is different from above-mentioned two technologies be can be when polymerization the different monomer of the importation of redundant technical facilities, promptly form homopolymer earlier, introduce successively second, third, the 4th or two or more monomeric mixture, thereby in reactor, directly obtain alloy heterogeneous, multiple polymers, but this technology is the multistage gaseous techniques of an elastic operation, the comparable nylon of product performance, PET, ABS, PVC.US 5,698,642 have had more advanced MZCR (multizone circulatingreactor) technology, and this technology has than catalloy technically and is a a progressive step, and it indicates that the ideal mixing of alloy and the disposable polymerization of solid solution in reaction form.Yet above technology all is the technology that is based upon on heterogeneous catalyst-Ziegler-Natta catalyst, has adopted gaseous techniques simultaneously when second goes on foot polymerization mostly.
Metallocene catalyst is the novel homogeneous catalyst that grew up in recent years, has single catalytic active center, and the molecular weight distribution that is generated is narrow, comonomer distribution is even, can generate syndiotactic copolymer, can make most of comonomers participate in polymerization; Thereby can realize the molecular designing of polymkeric substance.Thereby the metallocene catalyst catalysis in olefine polymerization, can be as requested, set in advance and generate polymer properties, thus more effective, telomerized polymer performance of composites more on purpose.Current, the method that the breadboard G. Collina of Montell equals among 1831 pages the Journal of AppliedPolymer Science of 1996 66 volumes is after carrying out the homopolymerization of PP, first with Ziegler-Natta catalyst water inactivation, and then directly add with alkyaluminoxane activatory r-EBTHZrCl
2Solution then carries out second third vapour phase polymerization.Yet this method is direct physical absorption metallocene catalyst r-EBTHZrCl in the polypropylene that generates
2, this method only can be used for gas phase process; In slurry process, will go out to have a strong impact on form owing to the drop of catalyzer, be difficult to form the ideal matrix material; This method also will be difficult to guarantee the uniform distribution of catalyzer simultaneously, thus the polymkeric substance that generates when being difficult to guarantee second step polymerization can with original polyolefine uniform mixing, thereby even in gas phase process, also be difficult to guarantee to obtain the ideal polymer composites.
Chung T.C. laboratory (Macromolecules, 1988,21:865-869) once reported a kind of boron-containing compound, this boron compound contains the reactive group borine, and can not make catalyst deactivation during with olefine reaction, under appropriate reaction conditions, reactive group can be changed into the polar functionalities group.The synthetic method of this boron-containing compound is to add 1 with being equipped with in the two-mouth bottle of constant pressure funnel, 5-hexadiene and tetrahydrofuran solution, the tetrahydrofuran solution of 9-BBN is joined in the constant pressure funnel, and it is splashed into 1 of continuous stirring, in the 5-hexadiene, dropwise, continue to stir, vacuum is removed tetrahydrofuran (THF) and unreacted 1 then, and the 5-hexadiene is collected colourless liquid.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite polyolefine material, the present invention is when propylene polymerization, can controllably in polyacrylic polymkeric substance, quantitatively introduce certain polar group, thereby metallocene catalyst is adsorbed in the polypropylene equably by chemical bond, further carries out the reaction of olefinic polymerization or copolymerization on this basis again.May slurry process can be used in the second step polymerization thus, and better form and mixed uniformly composite polyolefine material can be accessed, thus the matrix material of the tunable performance of realizing ideal.
The making of matrix material is mainly finished via four steps among the present invention: 1) at first the TiCl 4 catalyst of working load type carries out propylene and the monomeric polyreaction of boracic; 2) then with the polymkeric substance oxydrolysis of gained, obtain containing the polypropylene copolymer of certain hydroxyl; 3) then metallocene catalyst is carried on the polypropylene provided with hydroxyl group; 4) last in the polypropylene of gained other alkene of polymerization, form composite polyolefine material.
Specifically, preparation method of the present invention is as follows:
A) the monomeric polyreaction of propylene and boracic
Use slurry process, under loading type TiCl 4 catalyst and aluminum alkyls effect, carry out the monomeric polyreaction of propylene and boracic; This reaction is a solvent with one of benzene,toluene,xylene, hexane, heptane, pentane, octane, in 0-100 ℃ (being preferably 30-60 ℃), the propylene constant pressure directly feeds in the reactor continuously reacts, making the pressure in the reactor is under the 1-10 normal atmosphere (being preferably the 1-2 normal atmosphere), reacts to get polymkeric substance in 0.1-100 hour.
The ratio of catalyzer and solvent is 1 * 10
-4-1 * 10
-2G/ml.
The ratio of boracic monomer and solvent is 1 * 10
-3-1 * 10
-1G/ml.
The loading type TiCl 4 catalyst that the present invention is used is to be carrier loaded TiCl 4 catalyst by magnesium halide, and its charge capacity is counted 1-6% with Ti.
Magnesium halide carrier can be magnesium chloride, magnesium bromide, magnesium fluoride or magnesium iodide, and the carboxylicesters that can also add weight ratio 1-10% in the carrier is an internal electron donor, as diisobutyl phthalate, dibutyl phthalate or diethyl succinate.
This loading type TiCl 4 catalyst and aluminum alkyls ratio between the two carry out catalyzed reaction according to the ratio of Al/Ti=36-500.
The used boracic monomer of the present invention is the compound with following structure
N=0-16 wherein;
Can also add the phenylbenzene dimethylsilane, add-on is that Si/Al=0.01-1 adds according to the molar ratio of Al in its Si that contains and the alkylaluminoxane.
B) with the polymkeric substance oxydrolysis of step a gained
In the polymkeric substance of step a gained according to polymer weight ratio be the ratio of 0.1-10 add 5-40% sodium hydroxide the aqueous solution (preferable 20-30%) and according to polymer weight ratio be that superoxol (being preferably 10-20%) that the ratio of 1-10 adds the 2-40% tetrahydrofuran (THF) stirs and carried out oxydrolysis in 10min-40 hour, water, ethanol thorough washing, drying. obtain containing the polypropylene copolymer of hydroxyl.
How many additional proportions between above-mentioned polymkeric substance, sodium hydroxide solution, tetrahydrofuran solution and the alcohols is.
C) metallocene catalyst is carried on the polypropylene copolymer of step b gained
By will adding in the 1-50% alkylalumoxane solution in the 1-50% toluene aaerosol solution of polypropylene copolymer of step b gained with the part by weight of polymkeric substance 0.1-100, in 0-120 ℃, the 1-10atm pressure condition is reaction 0.1-100h down, filters washing; The metallocene catalysis agent solution (being preferably 0.1 μ mol/ml-10 μ mol/ml) of filtrate and 0.1 μ mol/ml-100 μ mol/ml is pressed the 0.1-1000 mixed, under 10-60 ℃, 1-5atm stirred 0.1-100 hour, with one of toluene, hexane, pentane, heptane thorough washing, filtration, drying get the polypropylene that load has metallocene catalyst.
The used alkylalumoxane solution of the present invention is that toluene, hexane, pentane are or/and n-heptane solution;
The aaerosol solution of the polypropylene copolymer that the present invention is used is that toluene, hexane, pentane are or/and the aaerosol solution of heptane;
The used metallocene catalyst of the present invention is toluene, hexane, pentane or/and n-heptane solution, and metallocene catalyst is the compound that contains following general formula:
R
n 1MR
m 2R
x 3；
R in the formula
1Be Me
2Si (Ind)
2, Me
2Si (2-Me-4-Ph-Ind)
2, Me
2Si (2-Me-Ind)
2, Me (Me
3Si) Si (2-Me-4-Ph-Ind)
2, Me
2Si (IndR
2)
2, Et (ind)
2, Me
2SiCp, MeCp, CpInd, Cp, Ph
2C (Cp) (Flu), Ph
2C (Cp) (2-Me
2NFlu) or Ph
2C (Cp) (2-MeOFlu);
Wherein: Cp is C
5H
5Ind is C
9H
7Ph is a phenyl ring; Me is CH
3
R in the formula
2, R
3Be Cl or Me; M is Zr, Ti, Hf or La; N=1-3, m=0-2, x=0-2;
D) other alkene of polymerization in the polypropylene of step c gained forms composite polyolefine material
With one of benzene,toluene,xylene, hexane, heptane, pentane, octane is solvent, 0.1-50% according to weight of solvent adds the product that step c makes, it is 1-10 (being preferably 5-10) normal atmosphere that continuous feeding alkene or alkene mixture make reaction pressure, in 20-100 ℃ (being preferably 50-80 ℃), reacted 10-300 minute, and got composite polyolefine material; The concentration that can also add the 1-30% of quantity of solvent before reaction is the alkylalumoxane solution of 0.5-2.5M.
Alkene that the present invention is used or alkene mixture refer to any two or more the mixture in ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, vinylbenzene or they.
Embodiment
The Ziegler-Natta catalyst preparation
Embodiment 1
With 24 gram MgCl
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 220mlTiCl4 then, and 3ml is a diisobutyl phthalate.Stir and heat up 110 ℃, handled 1.5 hours.Hexane wash obtains product 4 times.Ti content is 5.96%
Embodiment 2
With 24 gram MgCl
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 160mlTiCl4 then, and the 1.4ml dibutyl phthalate.Stir and heat up 110 ℃, handled 1.5 hours.Toluene wash obtains product 4 times, and Ti content is 3.38%
Embodiment 3
With 24 gram MgBr
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 30mlTiCl4 then, and the 0.4ml dibutyl phthalate.Stir and heat up 110 ℃, handled 1.5 hours.Heptane wash 4 times, hexane wash once obtains product then, and Ti content is 1.12%
The polyacrylic preparation of boracic
Embodiment 4
Get the 10L there-necked flask, add 1000ml toluene, add the n-heptane solution of the triethyl aluminum (TEA) of 2.5ml1.8M, add phenylbenzene dimethylsilane (DDS) and the 1 gram B-5-Hexenyl-9-BBN of 0.045mmol, stirring adds 0.1g embodiment 1 catalyzer down.0 ℃ feeds propylene gas, and reaction is 100 hours under 1 normal atmosphere, obtains polymkeric substance 2kg.
Embodiment 5
Get the 250ml there-necked flask, add 100ml toluene, add the n-heptane solution of the triethyl aluminum (TEA) of 4ml1.8M, add phenylbenzene dimethylsilane (DDS) and the 1 gram B-5-Hexenyl-9-BBN of 0.045mmol, stirring adds embodiment 2 catalyzer down.Heat up 40 ℃, feed propylene gas, reacted one hour.Obtain polymkeric substance 15g
Embodiment 6
Get 101 there-necked flasks, add 1000ml toluene, add triethyl aluminum (TEA) n-heptane solution of 62.5ml1.8M, add phenylbenzene dimethylsilane (DDS) and the 10 gram B-5-Hexenyl-9-BBN of 110mmol, stirring adds 1g embodiment 2 catalyzer down.Heat up 120 ℃ pressure 10 normal atmosphere.Feed propylene gas, reacted 0.1 hour.Obtain polymkeric substance 10g
Oxydrolysis
Embodiment 7
The NaOH solution that adds 10ml40% under-5 ℃ in embodiment 4 then adds the THF solution of 1000g2% hydrogen peroxide.Stirred 40 hours, water, ethanol thorough washing, drying obtains polypropylene provided with hydroxyl group.
Embodiment 8
The NaOH solution that adds 10ml40% under 0 ℃ in embodiment 5 then adds the THF solution of 30ml 30% hydrogen peroxide.Stirred 3 hours, water, ethanol thorough washing, drying obtains polypropylene provided with hydroxyl group.
Embodiment 9
The NaOH solution that adds 100ml 5% under 20 ℃ in embodiment 6 then adds the THF solution of 100g 40% hydrogen peroxide.Stir 10min, water, ethanol thorough washing, the dry filter washing obtains polypropylene provided with hydroxyl group.
The load of metallocene catalyst
Embodiment 10
Get 2 gram embodiment, 7 gained polypropylene provided with hydroxyl group and prepare in the still, add 4ml toluene, add the MAO toluene solution of 200ml 1% in 1000ml, 10atm, 120 ℃ were stirred 100 hours.Suction filtration, washing three times.The Cp that adds 2g 100 μ mol/ml then
2ZrCl
2Toluene solution, 10 ℃ of 5atm stirred 100 hours down.Suction filtration, with 300ml dimethylbenzene washing 6 times, suction filtration is dry to get catalyzer No. 1.
Embodiment 11
Get 2 gram embodiment, 8 gained polypropylene provided with hydroxyl group in 5000ml preparation bottle, add 100ml toluene, add the MAO toluene solution of 16ml 10%, be warmed up to 60 ℃, stirred 3 hours.Suction filtration, washing three times.The Cp that adds 2000g 0.1 μ mol/ml then
2ZrCl
2Toluene solution, stirred 3 hours.Suction filtration is used 300ml toluene wash 6 times, and suction filtration is dry to get catalyzer No. 2.
Embodiment 12
Get 20 gram embodiment, 9 gained polypropylene provided with hydroxyl group in 500ml preparation bottle, add 20ml toluene, add the MAO toluene solution of 20ml 50%, 0 ℃ of 1atm stirred 0.1 hour.Suction filtration, heptane wash three times.The Cp that adds 2g 100 μ mol/ml then
2ZrCl
2Xylene solution, 60 ℃ of 3atm stirred 0.1 hour.Suction filtration, with 300ml pentane washing 6 times, suction filtration is dry to get catalyzer No. 3.
Ethylene polymerization
Embodiment 13
Add 100ml toluene in the 500ml reactor, add the MAO toluene solution of the 2.5M of 1ml, add the 0.1g catalyzer No. 1,100 ℃ of 10atm stir and feed ethylene gas, react 50 minutes.
Embodiment 14
Add 100ml toluene in the 250ml there-necked flask, add the MAO toluene solution of the 1.8M of 30ml, add the 50g catalyzer No. 2,20 ℃ of 1atm stir and feed ethene, propylene mixed gas, react 10 minutes.
Embodiment 15
Add 100ml toluene in the 500ml reactor, add the MAO toluene solution of the 0.5M of 8ml, add the 0.1g catalyzer No. 3,60 ℃ of 6atm stir and feed ethylene gas, react 300 minutes.
Embodiment 16
Add 100ml toluene in the 500ml reactor, add the MAO toluene solution of the 0.5M of 8ml, add octene 2ml and 0.1g catalyzer No. 2,60 ℃ of 6atm stir and feed ethylene gas, answer 30 minutes.
Embodiment 17
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 4ml 1.4M, add the 0.2g catalyzer No. 1,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 18
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 6ml 1.4M, add the 0.2g catalyzer No. 1,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 19
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 4ml 1.4M, add the 0.2g catalyzer No. 2,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 20
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 6ml 1.4M, add the 0.2g catalyzer No. 2,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 21
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 4ml 1.4M, add the 0.2g catalyzer No. 3,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 22
Add 50ml toluene in the 250ml there-necked flask, add the MAO of 4ml1.4, add the 0.2g catalyzer No. 3,50 ℃ are stirred the feeding ethylene gas, reacted 20 minutes.
Embodiment 23
Add 50ml toluene in the 250ml there-necked flask, add 4ml 1.4MAO, be added in No. 1 catalyzer 0.2g that places in the air after 4 days, 50 ℃ were reacted 100 minutes, and obtained product 1.45g.
Polymerization results among table 1 embodiment
| Embodiment | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 |
| Catalyzer | 1 | 2 | 3 | 2 | 1 | 1 | 2 | 2 | 3 | 3 | 1 |
| MAO measures (mmol) | 2.5 | 54 | 4 | 4 | 5.6 | 8.4 | 5.6 | 8.4 | 5.6 | 8.4 | 5.6 |
| Active g/gcat.h atm | 1.2 | 2.2 | 1.1 | 6.8 | 8.7 | 12.75 | 19.8 | 32.25 | 32.4 | 48 | 4.35 |
| Increase specific viscosity η sp | 34.12 | 40.42 | 33.60 | 46.11 | 32.51 | 38.68 | 34.98 | 35.93 | 27.98 | 33.05 | -- |
| Mn | --- | ---- | --- | -- | -- | --- | 120389 | 70552 | 59232 | 61598 | -- |
| Mw | --- | ---- | --- | ---- | -- | --- | 344374 | 299165 | 443794 | 318615 | -- |
| Mv | --- | ---- | --- | --- | 306161 | 261958 | 361430 | 267520 | -- |
Claims (13)
1. method for preparing composite polyolefine material, key step is:
A) the monomeric polyreaction of propylene and boracic
Use slurry process, under loading type TiCl 4 catalyst and aluminum alkyls effect, carry out the monomeric polyreaction of propylene and boracic; This reaction is a solvent with one of benzene,toluene,xylene, hexane, heptane, pentane, octane, and in 0 ℃-100 ℃, the propylene constant pressure feeds continuously in the reactor that to keep reaction pressure be the 1-10 normal atmosphere, reaction times 0.1-100 hour, obtains polymkeric substance;
Described loading type TiCl 4 catalyst is to be carrier by magnesium halide, is Primary Catalysts with the titanium tetrachloride, and wherein Ti content is the loaded catalyst of 1-6%; This catalyzer and aluminum alkyls react according to the ratio of Al/Ti=36-500;
The ratio of catalyzer and solvent is 1 * 10
-4-1 * 10
-2G/ml;
The ratio of boracic monomer and solvent is: 1 * 10
-3-1 * 10
-1G/ml;
Described boracic monomer is characterized by the compound with following structure
N=0-16 wherein;
B) with the polymkeric substance oxydrolysis of step a gained
Add the aqueous solution of 5-40% sodium hydroxide in the polymkeric substance of step a gained, sodium hydroxide solution and polymer weight ratio are 1: 0.1-10; At-5-20 ℃ of superoxol that adds the 2-40% tetrahydrofuran (THF), tetrahydrofuran solution and polymer weight ratio are 1: 1-10, carry out oxydrolysis, and stirring 10min-40h, water or ethanol thorough washing, drying obtains containing the polypropylene copolymer of hydroxyl;
C) metallocene catalyst is carried on the polypropylene copolymer of step b gained
In the 1%-50% toluene aaerosol solution with the polypropylene copolymer of adding step b gained in the 1-50% alkylalumoxane solution, wherein alkylaluminoxane and copolymer soliquoid weight ratio are 1: 0.1-100, and in 0-120 ℃, the 1-10atm pressure condition reacted 0.1-100 hour down, filter washing; The metallocene catalysis agent solution of filtrate and 0.1 μ mol/ml-100 μ mol/ml is pressed 1: the 0.1-1000 mixed, 1atm-5atm stirred 0.1-100 hour down, with one of toluene, hexane, heptane thorough washing, filtration, drying obtain the polypropylene that load has metallocene catalyst;
Described alkylalumoxane solution is toluene, hexane, pentane or n-heptane solution;
The aaerosol solution of described polypropylene copolymer is the aaerosol solution of toluene, hexane, pentane or heptane;
Described metallocene catalyst is toluene, hexane, pentane or n-heptane solution, and metallocene catalyst is the compound that contains following general formula:
R
n 1MR
m 2R
x 3；
R in the formula
1Be Me
2Si (Ind)
2, Me
2Si (2-Me-4-Ph-Ind)
2, Me
2Si (2-Me-Ind)
2, Me (Me
3Si) Si (2-Me-4-Ph-Ind)
2, Me
2Si (IndR
2)
2, Et (ind)
2, Me
2SiCp, MeCp, CpInd, Cp, Ph
2C (Cp) (Flu), Ph
2C (Cp) (2-Me
2NFlu) or Ph
2C (Cp) (2-MeOFlu);
Wherein: Cp is C
5H
5Ind is C
9H
7Ph is a phenyl ring; Me is CH
3
R in the formula
2Or R
3Be Cl or Me; M is Zr, Ti, Hf or La; N=1-3, m=0-2, x=0-2;
D) other alkene of polymerization in the polypropylene of step c gained forms composite polyolefine material
With one of benzene,toluene,xylene, hexane, heptane, pentane, octane is solvent, 0.1-50% according to weight of solvent adds the product that step c makes, it is the 1-10 normal atmosphere that continuous feeding alkene or alkene mixture make reaction pressure, in 20-100 ℃, under the 1-10 normal atmosphere, reacted 10-300 minute, and got composite polyolefine material;
Described alkene or alkene mixture refer to any in ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, the vinylbenzene, perhaps their any two or more mixtures.
2. preparation method as claimed in claim 1 is characterized in that, also can add the phenylbenzene dimethylsilane among the step a, and add-on is that Si/Al=0.01-1 adds according to the ratio of Al in its Si that contains and the alkylaluminoxane.
3. preparation method as claimed in claim 1 is characterized in that, the magnesium halide carrier of loading type TiCl 4 catalyst is magnesium chloride, magnesium bromide, magnesium fluoride or magnesium iodide among the step a.
4. as claim 1 or 3 described preparation methods, it is characterized in that the carboxylicesters that adds weight ratio 1-10% among the step a in the carrier of loading type TiCl 4 catalyst is an internal electron donor.
5. preparation method as claimed in claim 4 is characterized in that, described carboxylicesters is diisobutyl phthalate, dibutyl phthalate or diethyl succinate.
6. preparation method as claimed in claim 1 is characterized in that, reaction pressure is the 1-2 normal atmosphere among the step a.
7. preparation method as claimed in claim 1 is characterized in that, temperature of reaction is 30-60 ℃ among the step a.
8. preparation method as claimed in claim 1 is characterized in that, concentration of sodium hydroxide solution is 20-30% among the step b.
9. preparation method as claimed in claim 1 is characterized in that, the superoxol concentration of tetrahydrofuran (THF) is 10-20% among the step b.
10. preparation method as claimed in claim 1 is characterized in that, the metallocene catalyst strength of solution among the step c is 0.1 μ mol/ml-10 μ mol/ml.
11. preparation method as claimed in claim 1 is characterized in that, the concentration that also adds the 1-30% of quantity of solvent in the steps d is the toluene solution of the alkylaluminoxane of 0.5-2.5M.
12. preparation method as claimed in claim 1 is characterized in that, reaction pressure is the 5-10 normal atmosphere in the steps d.
13. preparation method as claimed in claim 1 is characterized in that, temperature of reaction is 50-80 ℃ in the steps d.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186812A (en) * | 1996-12-30 | 1998-07-08 | 中国科学院长春应用化学研究所 | Preparation of polymer carrier metallocene catalyst |
| WO2000071587A1 (en) * | 1999-05-25 | 2000-11-30 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
| CN1347343A (en) * | 1999-04-21 | 2002-05-01 | 巴塞尔聚烯烃有限公司 | Catalyst system |
| WO2002062858A1 (en) * | 2001-02-06 | 2002-08-15 | Bp Chemicals Limited | High activity polyethylene catalysts prepared with borates reagents |
-
2004
- 2004-04-26 CN CNB2004100385123A patent/CN100390207C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186812A (en) * | 1996-12-30 | 1998-07-08 | 中国科学院长春应用化学研究所 | Preparation of polymer carrier metallocene catalyst |
| CN1347343A (en) * | 1999-04-21 | 2002-05-01 | 巴塞尔聚烯烃有限公司 | Catalyst system |
| WO2000071587A1 (en) * | 1999-05-25 | 2000-11-30 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
| WO2002062858A1 (en) * | 2001-02-06 | 2002-08-15 | Bp Chemicals Limited | High activity polyethylene catalysts prepared with borates reagents |
Non-Patent Citations (1)
| Title |
|---|
| synthesis of polyalcohols via ziegler-natta polymerization. T.C.Chung.macromolecules,Vol.21 . 1988 * |
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| CN1690092A (en) | 2005-11-02 |
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