CN1511853A - Lower isotactic polypropylene catalyst system, its preparing process and use - Google Patents
Lower isotactic polypropylene catalyst system, its preparing process and use Download PDFInfo
- Publication number
- CN1511853A CN1511853A CNA021600465A CN02160046A CN1511853A CN 1511853 A CN1511853 A CN 1511853A CN A021600465 A CNA021600465 A CN A021600465A CN 02160046 A CN02160046 A CN 02160046A CN 1511853 A CN1511853 A CN 1511853A
- Authority
- CN
- China
- Prior art keywords
- containing titanium
- reaction
- solids containing
- solids
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a catalyst system for producing lower isotactic polypropylene and its preparation process and use. The titanium-containing solid catalyst system is prepared through the following steps: preparing homogeneous solution with chloridizing reagent in organic solvent and electron donor-1 via complexing; preparing through reaction of the homogeneous solution and the organic solvent suspension of Mg(OC2H5)2; reacting the mixed solution of titanium compound and organic solvent and the carrier in the presence of electron donor-2; and finally adding alkylating reagent and co-catalyst. The catalyst system of the present invention can lower the isotactic degree of polypropylene and has greatly lowered titanium compound consumption.
Description
Invention field
The present invention relates to a kind of be used to produce polyacrylic catalyst system, Preparation Method And The Use, more particularly, relate to a kind of catalyst system, Preparation Method And The Use that is used to produce than LIPP.
Prior art
Behind the propylene polymerization, because the different distributions of pending methyl group on polypropylene molecular chain produced isotactic (IPP), three kinds of different steric configurations of rule (SPP) and random (APP).Catalyst for polymerization of propylene not only requires high reactivity, but also requires highly-solid selectively, or high stereospecificity.
Polyacrylic different steric configuration plays an important role to its performance.High isotactic polypropylene product has higher structural strength, but along with the polypropylene degree of isotacticity is more and more higher, its inherent shortcoming such as elasticity is low, poor toughness, low temperature embrittlement, machine-shaping difficulty etc. have just become increasingly conspicuous.Sometimes have to add the material of some good toughness such as rubber, polyethylene, Atactic Polypropelene etc. and carry out modification in order to obtain some specified property in actual applications.And Atactic Polypropelene, it is the by product of isotatic polypropylene production normally, it has less molecular weight, higher surface viscosity, lower softening temperature, at hot-melt adhesive, rubber and plastic is material modified as fields such as water-proof material, blend master batch materials wide application.But along with the development of propene polymer production technique, the atrophy day by day of by-product Atactic Polypropelene apparent availability, some did the industry faces stopping production of raw material or the poverty-stricken selection of changing the line of production with it originally.
The steric configuration of LIPP molecular chain has high isotactic and random two kinds of configurations concurrently, high isotactic chain link is a rigid region, random chain link is a flexible region, it is a kind of thermoplastic elastomer (s), can have some advantage of high isotactic and Atactic Polypropelene concurrently, simultaneously avoid both some shortcomings again, thereby have the market outlook that attract people's attention.
The performance of LIPP is except with its molecular weight size and be distributed with the substantial connection, along with the ratio of isotactic in its molecular chain steric configuration and random two kinds of configurations is different and have than big-difference.The catalyst for polymerization of propylene of polypropylene molecular chain steric configuration or degree of isotacticity could be regulated and control to searching in a big way preparation method is the target that the dealer lays siege to always.
Having known the PP structure that luxuriant and derivative and MAO (poly-methylaluminoxane) are formed by some meso transition metal homogeneous phase soluble catalyst system obtains as at random, can make polypropylene [referring to for example: Takeshi Shiono based on random configuration, Hideshi Uchino and KazuoSoga, Polymer Bulletin 21,19-21 (1989)].The PP that is obtained by heterogeneous Ziegler-Natta carried catalyst contains the more block thing of being made up of isotactic chain link and random chain link, promptly has certain degree of isotacticity [referring to for example: Bermhard Rieger and James C.W.Chien, PolymerBulletin 21,155-163 (1989)].
V.Busico and colleague thereof propose with MgCl according to the effect of interior alkali and outer alkali
2There are two class catalytic active centers in the Ti base Ziegler-Natta catalyst of making carrier.(1) the isolated monokaryon titanium that two chlorine rooms are arranged that does not contain electron donor is non-oriented active center, can obtain APP.(2), contain the double-core or the multinuclear titanium (Ti in a chlorine room by the ligand bridge joint
2Cl
6) be the oriented active center, can obtain IPP[referring to for example: V.Busico, P.Corradini, L.De Martino etc., Makromol.Chem.187,1115,1986].In view of the above can by change the means such as Preparation of catalysts technology, composition, prescription of regulating are regulated or control catalyst in the kind and the quantity of two class catalytic active centers, thereby obtain in a big way, to regulate and to control the low isotactic catalyst for polymerization of propylene of polypropylene molecular chain steric configuration or degree of isotacticity.
Japanese Patent JP 59,22,311, JP 59,43,008, JP 01,236,203, JP 63,110,202; European patent EP 423,786; World patent WO 93,00320, WO 88,09348 grades have been reported LIPP (or being called Atactic Polypropelene or amorphous polypropylene) Preparation of catalysts method.Catalyst activity was lower when the catalyzer that uses above-mentioned patented method to prepare was used for propylene polymerization, mostly less than 1 * 10
4The gPP/g catalyzer, isotactic index (polymkeric substance is insoluble to the percentage composition of the heptane part of boiling) is higher, is generally 50～65%, and molecular weight is less, is 1 * 10
4～5 * 10
4
Chinese patent application 95116508.9 disclosed LIPP catalyzer have the catalytic activity height, are 3.0 * 10
4～6.0 * 10
4The gPP/g catalyzer, the polymkeric substance isotactic index is low, is 13～30%, its nucleus magnetic resonance (NMR)
13The mmmm% sequence distribution probability of C is 55～60%, and molecular weight is higher, is 3.0 * 10
4～8.0 * 10
4, catalyzer long service life, characteristics such as hydrogen regulation performance is good.
But the polypropylene that obtains when the catalyzer of patented method preparation is used for propylene polymerization thus still has higher degree of isotacticity (this point can be 55～60% to find out by its mmmm% sequence distribution probability), low-temperature pliability is poor slightly, in the application scenario of the good low-temperature performance of needs, still be difficult to win in the water-proof materials such as the roof that uses as northern China, highway, warehouse, bridge and use.
Therefore, this area still needs to develop the propylene polymerization catalyzer that can further reduce polyacrylic degree of isotacticity.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor according to V.Busico and colleague thereof propose with MgCl
2There is the theory of two class catalytic active centers in the Ti base Ziegler-Natta catalyst of making carrier, by changing some processing condition, composition and prescription, as add alkylating reagent and reduce the titanium compound consumption and wait and promote to form more non-directional active centre species and quantity, thereby develop the catalyst system that can obtain than LIPP.The present invention is based on this is accomplished.
Therefore, an object of the present invention is to provide a kind of catalyst system that is used to produce than LIPP, compare with the catalyst system of prior art, this catalyst system contains the titanium of greatly reduction amount and uses the polypropylene of this system preparation to have lower degree of isotacticity.
Another object of the present invention provides a kind of method for preparing the solids containing titanium catalyzer in the above-mentioned catalyst system.
A further object of the present invention provides the method for a kind of production than LIPP.
One aspect of the present invention provides a kind of catalyst system that is used to produce than LIPP, and it comprises solids containing titanium catalyzer and promotor.
The present invention provides a kind of method for preparing the solids containing titanium catalyzer in the above-mentioned catalyst system on the other hand.
It is a kind of with the method for liquid phase noumenal method preparation than LIPP that one side more of the present invention provides.
These and other purposes of the present invention, feature and advantage will become clearer after reading whole specification sheets.
Detailed Description Of The Invention
The present invention is described in detail as follows.
The catalyst system that the present invention is used to produce than LIPP comprises solids containing titanium catalyzer and promotor.Described solids containing titanium catalyzer is made by the method that comprises the steps:
1) preparation of chlorination reagent complex compound: in organic solvent, carry out complex reaction with electron donor-1 (E-1) with anhydrous chlorides of rase reagent, generate homogeneous solution, wherein [E-1]: the mol ratio of [chlorination reagent] is that the temperature of 1: 1～1: 8 and complex reaction is 0～30 ℃;
2) preparation of carrier: the homogeneous solution and the Mg (OC of the chlorination reagent complex compound that step 1) is made
2H
5)
2Organic solvent suspension reaction make carrier, wherein [Mg (OC
2H
5)
2]: the mol ratio of [chlorination reagent] is 1: 0.3～1: 3.0, and the preparing carriers temperature is that 50～100 ℃ and reaction times are 1～6 hour;
3) preparation of carried catalyst solids: in the presence of electron donor-2 (E-2), will be by step 2) carrier that makes and the reaction of the mixed solution of titanium compound and organic solvent obtain titaniferous carried catalyst solids, wherein [Mg]: [Ti] mol ratio is 1: 0.3～1: 3.0, [organic solvent]: [Ti] mol ratio is 40: 1～4: 1 and [E-2]: [Ti] mol ratio is 0.05: 1～0.8: 1;
4) in the titaniferous carried catalyst solids that alkylated reaction: alkylating reagent is joined above-mentioned steps 3) makes, wherein [alkylating reagent]: [Ti] mol ratio is 0.04: 1～0.55: 1, obtains of the present invention than LIPP solids containing titanium catalyzer.
Chlorination reagent used in solids containing titanium Preparation of catalysts step 1) of the present invention can be AlCl
3, CCl
4, SiCl
4, POCl
3, PCl
5Deng, preferred AlCl
3
Used electron donor-1 can be aromatic monocarboxylate's ester or silicoorganic compound in solids containing titanium Preparation of catalysts step 1) of the present invention.Described aromatic monocarboxylate's ester is ethyl benzoate, propyl benzoate, butyl benzoate or the different monooctyl ester of phenylformic acid etc.Described silicoorganic compound are tetraethoxy, methyltrimethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane or dimethoxydiphenylsilane etc.
In solids containing titanium Preparation of catalysts step 1) of the present invention, [E-1]: the mol ratio of [chlorination reagent] is 1: 1～1: 8, is preferably 1: 2～1: 4, described step carries out under 0～30 ℃ temperature-
In solids containing titanium Preparation of catalysts step 2 of the present invention) in, [Mg (OC
2H
5)
2]: the mol ratio of [chlorination reagent] is 1: 0.3～1: 3.0, is preferably 1: 0.5～1: 0.8, and described step was carried out under preferred 80～90 ℃ temperature 1～6 hour at 50～100 ℃.
Used electron donor-2 is methyltrimethoxy silane, ethyl trimethoxy silane, phenyl methyl dimethoxy silane, phenyl methyl diethoxy silane, methylcyclohexyl dimethoxy silane, diisopropyl dimethoxy silane or two and butyl dimethoxy silane etc. in solids containing titanium Preparation of catalysts step 3) of the present invention.In solids containing titanium Preparation of catalysts step 3) of the present invention, electron donor-2 also can be in step 2) carrier that makes and titanium compound reaction add in the reaction system and make its further reaction 0.5～2 hour after 0.5～2 hour.
Used titanium compound can be formula Ti (OR) in solids containing titanium Preparation of catalysts step 3) of the present invention
nX
4-nShown titanium compound, wherein R is C
1～C
9Alkyl, X are halogen such as fluorine, chlorine, bromine or iodine, preferred chlorine or bromine, and chlorine most preferably, n is 0 to 4 integer.
In solids containing titanium Preparation of catalysts step 3) of the present invention, [E-2]: [Ti] mol ratio is 0.05: 1～0.8: 1, preferred 0.1: 1～0.3: 1, [Mg]: [Ti] mol ratio is 1: 0.3～1: 3.0, be preferably 1: 0.5～1: 1.3, [organic solvent]: [Ti] mol ratio is 40: 1～4: 1, and described step is at 60～110 ℃, carries out 1～4 hour under preferred 80～90 ℃.
In solids containing titanium Preparation of catalysts step 1) of the present invention～3) in, normally used organic solvent is C
8～C
18Side chain or straight-chain paraffin or replacement or substituted arene not.Object lesson has dimethylhexane, tetramethyl-hexane, the C of decane, various isomeries
11～C
18Alkane such as normal paraffin, or aromatic hydrocarbons or substituted arene such as toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichlorobenzene preferably use toluene or chlorobenzene as organic solvent.
Alkylating reagent used in solids containing titanium Preparation of catalysts step 4) of the present invention can be formula R
1 3Alkylaluminium cpd shown in the Al, wherein R
1Can be the branched-chain or straight-chain alkyl that is selected from ethyl, propyl group, sec.-propyl, isobutyl-, amyl group, hexyl or iso-octyl etc.In solids containing titanium Preparation of catalysts step 4) of the present invention, [alkylating reagent]: [Ti] mol ratio is 0.04: 1～0.55: 1, preferred 0.1～0.25.Step 4) was carried out under preferred 80～90 ℃ temperature 1～4 hour at 60～110 ℃.
In solids containing titanium Preparation of catalysts method of the present invention, carrying the titanium process can once carry out in step 3), also can carry out in two steps, so that it is more abundant to carry titanium.When carrying titanium with two steps, usually titanium compound used to be loaded with is divided into two parts, a copy of it uses in step 3), uses after the alkylated reaction of another part in step 4).
Being used for producing the promotor that the catalyst system than LIPP uses in the present invention can be that general formula is R
mAlX
3-mAikyl aluminum halide, R is C in the formula
1～C
9Alkyl, X are halogen such as fluorine, chlorine, bromine or iodine, preferred chlorine or bromine, and chlorine most preferably, m is the integer of 1-3.The specific examples of operable aikyl aluminum halide has diethylaluminum chloride, ethylaluminium dichloride, triethyl aluminum, tri-butyl aluminum and triisobutyl aluminium etc., most preferably triisobutyl aluminium.When carrying out propylene polymerization with liquid phase noumenal method, the consumption of promotor is 50～1500 with titaniferous molar ratio computing in contained aluminium in the promotor and the solids containing titanium catalyzer, preferred 200～500.
Of the present invention is 1.6～4.0 * 10 than the catalytic activity of low grade polypropylene catalyst series when the liquid phase noumenal method propylene polymerization
4The gPP/g catalyzer; Polymkeric substance isotactic index (the heptane insoluble part of boiling content) is 10～20 weight %, its nucleus magnetic resonance (NMR)
13The mmmm% sequence distribution probability of C is 40～53%, and weight-average molecular weight is 8 * 10
4～12 * 10
4
Of the present invention than low grade polypropylene catalyst series in, [Mg]: [Ti] mol ratio is 1: 0.3～1: 3.0, preferred 1: 0.5～1: 1.3, this has compared with prior art reduced the consumption of titanium compound significantly, thereby greatly reduce the Catalyst Production cost, alleviated pollution environment.
Of the present invention than low grade polypropylene catalyst series long service life compared with prior art, stable performance, hydrogen transfers effect good during polymerization.
Of the present invention simple than the low grade polypropylene catalyst series preparation method, easy and simple to handle, raw materials cost is low, favorable reproducibility, and stability is high, realizes suitability for industrialized production easily.
Of the present inventionly can be used for preparing polypropylene than low grade by the common known method in this area than the low grade polypropylene catalyst catalyst system, described method for example has slurry polymerization, solution polymerization, liquid-phase bulk polymerization etc., preferred liquid phase mass polymerization.
The method of using always and knowing that is than low grade polypropylene catalyst series and by its analysis test method that polymkeric substance adopted that makes of the present invention:
(1) isotactic index: adopt the heptane dissolution method of boiling.The granulated samples of drying constant weight is refluxed in the heptane that boils after the dissolving, and the mass percent of insoluble part is an isotactic index.
(2) molecular weight and distribution thereof: adopt the U.S. 150C of Water company type GPC instrument to measure.Condition determination is: (series connection of 7.8 * 300mm), four posts, 135 ℃ of column temperatures, solvent are orthodichlorobenzene to Styragel HT post, flow velocity 1ml/min, sample concentration 0.25 weight %, sample size 200ml.
(3)
13C-NMR measures: adopt Bruker AM-300 type nuclear magnetic resonance analyser, orthodichlorobenzene is made solvent, 120 ℃ of mensuration.
(4) ultimate analysis of catalyzer: adopt the inductively coupled plasma emission spectrometer (ICP) of U.S. TJA company, sample dissolves, measures behind the constant volume with acid.
(5) catalyst specific surface and pore distribution: specific surface adopts the BET method to measure.Pore distribution adopts the BJH method to measure.
Following examples will be further specified the preparation method than low grade polypropylene catalyst series of the present invention, but scope of the present invention is not so limited.
Embodiment 1Preparation and polymerization than low grade polypropylene catalyst
(1) complex reaction of aluminum chloride
To the process thorough drying, pump drainage in the 500ml there-necked flask with refining nitrogen replacement, adds 4.28g Aluminum chloride anhydrous and 56ml toluene (a) under nitrogen protection repeatedly.In the constant voltage addition funnel, add 4.04ml phenylbenzene dimethoxy silicon (DDS) and 28ml toluene (b).Open to stir, under 0～15 ℃, (b) is added drop-wise in (a) in 25～30 minutes.Be warming up to 30 ℃ after drip finishing, isothermal reaction 1 hour obtains the even complex solution (c) of aluminum chloride.
(2) preparation carrier
The reactor of band strainer of customization after high purity nitrogen is fully replaced, is added 9.17g Mg (OC under nitrogen protection
2H
5)
2With 63ml chlorobenzene (d).Open and stir, be warming up to 80 ℃, in 30～45 minutes (c) is added dropwise in (d), insulation reaction was stirred 1 hour at 80 ℃ in dropping end back, and cool to room temperature with 50ml toluene wash and filtration totally 3 times, obtains carrier (e) at every turn.
(3) preparation titaniferous carried catalyst solids
In above-mentioned carrier (e), add 50ml toluene and 8.81ml TiCl
4, open and stir, be warming up to 80 ℃, reacted 1 hour.Add 50ml toluene again and 2.23ml methylcyclohexyl dimethoxy silane is warming up to 80 ℃, stirring reaction 1 hour obtains titaniferous carried catalyst solids (f).
(4) alkylated reaction
In above-mentioned titaniferous carried catalyst solids (f), add the 2.71ml triisobutyl aluminium, 80 ℃ of following stirring reactions 1 hour.Add TiCl once more with the equivalent first time
4, continued stirring reaction 1 hour at 80 ℃.Finish reaction.With 50ml toluene wash and filtration 1 time, fluid temperature remains 60 ℃ during filtration.Cool to room temperature is with the washing of 50ml normal hexane, filter 23.Drying is weighed, and obtains catalyzer (g).
(5) liquid phase noumenal method propylene polymerization
5L stainless steel polymeric kettle is vacuumized the thorough pump drainage displacement of inflated with nitrogen three times under 80 ℃.Add the 2.1L propylene successively, stoichiometric triisobutyl aluminium (al-ti ratio 400), the above-mentioned catalyzer that makes of about 20mg (g), 2.0L hydrogen and remaining 1.4L propylene.Be warming up to 70 ℃, low whipping speed 300r/min reaction down finishes reaction after 2 hours.Obtain LIPP resin 432g, catalytic activity 21600gPP/g catalyzer, isotactic index 12.4%,
13The mmmm% of C-NMR is 48.6%, molecular weight 8.9 * 10
4, dispersion index D is 6.04.
Embodiment 2～11
Repeat the program of embodiment 1 step 1～4, that different is change chlorination reagent as shown in table 1 below, TiCl
4, E-2 proportioning, prepare catalyzer 2～11 thus.
Reference examples 1
According to Chinese patent application 95116508.9 embodiment 1 preparation comparative catalyst 1, wherein used chlorination reagent, TiCl
4, E-2 proportioning also be shown in the following table 1.
Table 1 is than the embodiment of low grade polypropylene catalyst preparation
| Embodiment | ????AlCl 3 | ???TiCl 4 * | ????E-2 |
| ????g | ????ml | ????ml | |
| ????1 | ????4.28 | ????8.81 | ????2.23 |
| ????2 | ????7.48 | ????10.1 | ????1.75 |
| ????3 | ????10.69 | ????11.5 | ????1.27 |
| ????4 | ????5.35 | ????12.8 | ????0.80 |
| ????5 | ????8.55 | ????14.1 | ????0.32 |
| ????6 | ????6.41 | ????6.17 | ????3.18 |
| ????7 | ????4.28 | ????8.81 | ????2.23 |
| ????8 | ????10.69 | ????0.88 | ????1.27 |
| ????9 | ????5.35 | ????7.49 | ????0.80 |
| ????10 | ????8.55 | ????3.53 | ????0.32 |
| ????11 | ????10.69 | ????11.5 | ????1.27 |
| Reference examples 1 | ????7.5 | ????25.0 | ????2.1 |
*Data are for adding for the first time TiCl in the table
4Amount, add for the second time TiCl
4Amount with for the first time identical.
To embodiment 2～5 prepared carrying out ultimate analysis and measure surface properties than low grade polypropylene catalyst, the result is as shown in table 2 below.
Table 2. is than low grade polypropylene catalyst ultimate analysis and surface properties
| Embodiment | Ultimate analysis, % | Surface properties | ||||||
| ??Ti | ??Mg | ??Si | ??Al | Surface-area m 2/g | Relation conefficient | Mean pore size A | Pore volume g/ml | |
| 2 | ??4.43 | ??14.45 | ?0.26 | ?0.61 | ??17.41 | ??0.999 | ??18.46 | ??4.000 |
| 3 | ??4.22 | ??15.79 | ?0.13 | ?0.96 | ??22.78 | ??0.998 | ??16.93 | ??5.232 |
| 4 | ??3.95 | ??16.14 | ?0.13 | ?0.43 | ??116.3 | ??0.999 | ??27.976 | ??26.71 |
| 5 | ??3.57 | ??16.30 | ?0.08 | ?0.74 | ??95.94 | ??0.999 | ??28.137 | ??22.04 |
Use embodiment 6～8 prepared than low grade polypropylene catalyst as preparation polypropylene as described in embodiment 1 step 5, and measure prepared polyacrylic molecular weight and distribution thereof, the gained result is shown in the following table 3 with the result of embodiment 1.
Polyacrylic molecular weight and distribution thereof that table 3. makes than low grade polypropylene catalyst
| Embodiment | ?Mn ?10 4 | ?Mw ?10 4 | Molecular weight distribution | η Intrinsic | Molecular level part 10 4 | ||
| Peak value | ＜3％ | ?＞10％ | |||||
| ?1 | ?1.48 | ?8.95 | ?6.04 | ?0.836 | ?4.77 | ?31.3 | ?25.2 |
| ?6 | ?2.09 | ?12.0 | ?5.74 | ?1.04 | ?5.46 | ?22.6 | ?29.3 |
| ?7 | ?1.89 | ?11.0 | ?5.82 | ?0.984 | ?6.33 | ?7.21 | ?32.3 |
| ?8 | ?2.58 | ?8.46 | ?3.27 | ?0.820 | |||
The catalyzer that uses embodiment 2～5,9～11 and reference examples 1 is as carrying out the polymerization of propylene as described in embodiment 1 step 5.To activity of such catalysts and resulting polymers
13C-NMR mmmm% and isotactic index are measured, and the result is shown in the following table 4 with embodiment 1 and embodiment 8.
Table 4. is than the activity and the stereoselectivity of low grade polypropylene catalyst
| Embodiment | Active | mmmm | ?mm | ?rr | Isotactic index |
| ?1 | ?21600 | ?48.6 | ?61.8 | ?17.1 | ?12.4 |
| ?2 | ?25692 | ?16.0 | |||
| ?3 | ?28528 | ?44.4 | ?59.3 | ?17.7 | |
| ?4 | ?36574 | ?48.4 | ?62.0 | ?16.5 | ?11.0 |
| ?5 | ?29070 | ?50.3 | ?64.1 | ?16.0 | ?19.0 |
| ?8 | ?28900 | ?50.0 | ?63.2 | ?16.3 | ?11.0 |
| ?9 | ?16000 | ?52.9 | ?65.8 | ?15.4 | ?15.1 |
| ?10 | ?16700 | ?52.6 | ?65.7 | ?14.9 | |
| ?11 | ?27778 | ?51.3 | ?64.3 | ?15.6 | ?15.0 |
| Reference examples 1 | ?32000 | ?59.4 | ?13.0 |
Claims (12)
1. solids containing titanium catalyzer that is used to produce than LIPP is prepared by a method comprising the following steps:
1) preparation of chlorination reagent complex compound: in organic solvent, carry out complex reaction with electron donor-1 (E-1) with anhydrous chlorides of rase reagent, generate homogeneous solution, wherein [E-1]: the mol ratio of [chlorination reagent] is 1: 1～1: 8, be preferably 1: 2～and the temperature of 1: 4 and complex reaction is 0～30 ℃;
2) preparation of carrier: the homogeneous solution and the Mg (OC of the chlorination reagent complex compound that step 1) is made
2H
5)
2Organic solvent suspension reaction make carrier, wherein [Mg (OC
2H
5)
2]: the mol ratio of [chlorination reagent] is 1: 0.3～1: 3.0, be preferably 1: 0.5～1: 0.8 and preparing carriers temperature are 50～100 ℃, are preferably 80～90 ℃, the reaction times is 1～6 hour;
3) preparation of carried catalyst solids: in the presence of electron donor-2 (E-2), will be by step 2) carrier that makes and the reaction of the mixed solution of titanium compound and organic solvent obtain titaniferous carried catalyst solids, wherein [Mg]: [Ti] mol ratio is 1: 0.3～1: 3.0, be preferably 1: 0.5～1: 1.3, [organic solvent]: [Ti] mol ratio is 40: 1～4: 1 and [E-2]: [Ti] mol ratio is 0.05: 1～0.8: 1, preferred 0.1: 1～0.3: 1; With
4) in the titaniferous carried catalyst solids that alkylated reaction: alkylating reagent is joined above-mentioned steps 3) makes, wherein [alkylating reagent]: [Ti] mol ratio is 0.04: 1～0.55: 1, obtains of the present invention than LIPP solids containing titanium catalyzer.
2. solids containing titanium catalyzer according to claim 1, wherein said organic solvent are C
8～C
18Side chain or straight-chain paraffin or replacement or substituted arene not, preferred decane, the dimethylhexane of various isomeries, tetramethyl-hexane, C
11～C
18Normal paraffin, toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichlorobenzene, more preferably toluene or chlorobenzene.
3. solids containing titanium catalyzer according to claim 1, wherein said electron donor-the 1st, aromatic monocarboxylate's ester, preferred ethyl benzoate, propyl benzoate, butyl benzoate or the different monooctyl ester of phenylformic acid, or silicoorganic compound, preferred tetraethoxy, methyltrimethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane or dimethoxydiphenylsilane; Described electron donor-2 is methyltrimethoxy silane, ethyl trimethoxy silane, phenyl methyl dimethoxy silane, phenyl methyl diethoxy silane, methylcyclohexyl dimethoxy silane, diisopropyl dimethoxy silane or second, isobutyl dimethoxy silane; And described chlorination reagent is AlCl
3, CCl
4, SiCl
4, POCl
3, PCl
5
4. solids containing titanium catalyzer according to claim 3, wherein said chlorination reagent are AlCl
3
5. solids containing titanium catalyzer according to claim 1, wherein said titanium compound are formula Ti (OR)
nX
4-nShown titanium compound, wherein R is C
1～C
9Alkyl, X are halogen such as fluorine, chlorine, bromine or iodine, preferred chlorine or bromine, and chlorine most preferably, n is 0 to 4 integer.
6. solids containing titanium catalyzer according to claim 1, wherein said alkylating reagent are R
1 3Alkylaluminium cpd shown in the Al, R in the formula
1For being selected from the branched-chain or straight-chain alkyl of ethyl, propyl group, sec.-propyl, isobutyl-, amyl group, hexyl or iso-octyl etc.
7. solids containing titanium catalyzer according to claim 1, the preparation temperature of wherein said titaniferous carried catalyst solids is 60～110 ℃, preferred 80～90 ℃, the reaction times is 1～4 hour.
8. according to claim 1 or 7 described solids containing titanium catalyzer, wherein when the preparation of titaniferous carried catalyst solids electron donor-2 in step 2) carrier that makes and titanium compound reaction add in the reaction system and make its further reaction 0.5～2 hour after 0.5～2 hour.
9. solids containing titanium catalyzer according to claim 1, the temperature of wherein said alkylating reagent and the reaction of titaniferous carried catalyst solids is 60～110 ℃, preferred 80～90 ℃, the reaction times is 1～4 hour.
10. solids containing titanium catalyzer according to claim 1, wherein titanium compound once adds in step 3), or is divided into two parts of uses afterwards of the alkylated reaction in step 3) and in step 4) respectively.
11. a catalyst system that is used to produce than LIPP comprises according to each described solids containing titanium catalyzer and a kind of promotor in the claim 1～10, wherein said promotor is a general formula R
mAlX
3-mAikyl aluminum halide, R is C in the formula
1～C
9Alkyl, X are halogen, and m is 50～1500 by 1 to 3 the integer and the consumption of described promotor with titaniferous molar ratio computing in contained aluminium in the promotor and the solids containing titanium catalyzer, preferred 200～500.
12. a method of passing through with the liquid phase noumenal method polypropylene is wherein used catalyst system according to claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02160046 CN1243031C (en) | 2002-12-31 | 2002-12-31 | Lower isotactic polypropylene catalyst system, its preparing process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02160046 CN1243031C (en) | 2002-12-31 | 2002-12-31 | Lower isotactic polypropylene catalyst system, its preparing process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1511853A true CN1511853A (en) | 2004-07-14 |
| CN1243031C CN1243031C (en) | 2006-02-22 |
Family
ID=34237733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02160046 Expired - Fee Related CN1243031C (en) | 2002-12-31 | 2002-12-31 | Lower isotactic polypropylene catalyst system, its preparing process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1243031C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665211A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Supported composite catalyst for producing high melt strength polypropylene |
-
2002
- 2002-12-31 CN CN 02160046 patent/CN1243031C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665211A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Supported composite catalyst for producing high melt strength polypropylene |
| CN103665211B (en) * | 2012-09-20 | 2016-03-16 | 中国石油化工股份有限公司 | A kind of loading type composite catalyst for the production of high melt strength, propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1243031C (en) | 2006-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI88926C (en) | FOER FARING FOR FRAMSTAELLNING AV EN CATALYST COMPONENT FOR POLYMERIZATION OF OILFINER | |
| CN1146585C (en) | catalyst component and catalyst for olefin polymerization | |
| CN1162451C (en) | Catalyst components for the polymerization of olefins | |
| CN1095848C (en) | Supported ionic catalyst composition | |
| CN1726080A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN1071338C (en) | Highh activity polyethylene catalysts | |
| CN1262693A (en) | Prepolymerized catalyst components for polymerization of olefins | |
| CN1236372A (en) | Components and catalysts for the polymerization of olefins | |
| CN1512915A (en) | Improved olefin polymerization catalyst compositions and method of preparation | |
| CN1721455A (en) | Catalyst components for the polymerization of olefins | |
| RU2055080C1 (en) | Catalyst for propylene polymerization, catalytic system for propylene polymerization and a method of polypropylene producing by propylene polymerization | |
| CN1037106C (en) | Polymetallic catalysts, method of preparing and polymers produced thereby | |
| CN1958620A (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN1306544A (en) | Catalyst and components for olefin polymerization | |
| CA1311741C (en) | Preparation of olefin polymerization catalyst component | |
| CN104903359A (en) | Process of polymerization catalyst production with controlled catalyst properties and use of same in olefin polymerizations | |
| CN1856512A (en) | Self limiting catalyst composition and propylene polymerization process | |
| CN102603932B (en) | Solid catalyst component and catalyst for olefinic polymerization | |
| CN1264393A (en) | High activity polyethylene catalysts | |
| CN1049357A (en) | Elastomeric propylene copolymers and process for manufacturing them in gas phase thereof | |
| CN1035007C (en) | Ziegler-natta catalyst | |
| CN103788252A (en) | Catalyst solid ingredient, catalyst containing catalyst solid ingredient and use of catalyst in olefin polymerization | |
| CN1400979A (en) | Pre-polymerized catalyst components for the polymerization of olefins | |
| CN101054424A (en) | Method for preparing solid catalyst in olefin polymerization catalyst | |
| CN1302023C (en) | Magnesium dichloride-ethanol adducts and catalyst components obtained therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |