CN1067691C - Carried polypropylene catalyst - Google Patents
Carried polypropylene catalyst Download PDFInfo
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- CN1067691C CN1067691C CN97112005A CN97112005A CN1067691C CN 1067691 C CN1067691 C CN 1067691C CN 97112005 A CN97112005 A CN 97112005A CN 97112005 A CN97112005 A CN 97112005A CN 1067691 C CN1067691 C CN 1067691C
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Abstract
The present invention relates to a polypropylene solid catalyst prepared from titanium compounds and internal donors, which are loaded on active magnesium chloride. The magnesium content of the catalyst is from 15% to 25% by weight, the titanium content is from 1.0% to 5.0% by weight, and the internal donor content is from 8% to 15% by weight. The internal donors comprise ester shown in a formula (I) and ether shown in a formula (II). When the catalyst is used for the polymerization of propylene, products with the isotacticity index of 93.7% to 98.9% can be obtained, and the isotacticity index of the products can be adjusted.
Description
The present invention is a kind of carried polypropylene catalyst, specifically, is the polypropylene solid catalyst of load titanium compound on the active chlorine species magnesium.
From USP4,298,718, USP 4,495,388 propose with magnesium halide in active as Ziegler-natta catalyst component carrier after, the high efficiency load type catalyzer is able to fast development.This type of solid catalyst mainly is made up of the titanium and the internal electron donor compound that are carried on the active magnesium chloride, when internal electron donor is ester compound, during polymerization, must be under the effect of promotor aluminum alkyls, and the adding external electron donor just can obtain high degree of isotacticity product, as USP5,068,213 disclose a kind of polyolefin catalyst, with the titanium chloride and the internal electron donor phthalic ester that load on the active magnesium chloride is solid catalyst, the external electron donor that adds aluminum alkyls and two ethers during polymerization, obtained high polymerization activity, wherein be the catalyzer of internal electron donor preparation, add triethyl aluminum and diether compound during polymerization, can make degree of isotacticity and be 92% or 95% polypropylene product with the diisobutyl phthalate.EP 0362705A2 also has similar report, this patent is that internal electron donor prepares solid catalyst with the ester, be external electron donor with multiple diether compound during polymerization, for the propylene polymerization under the identical conditions, gained polymerization activity and degree of isotacticity all have than big-difference.
In addition, can ether compound be that internal electron donor prepares solid catalyst also, do not add external electron donor when being characterized in polymerization and can obtain high degree of isotacticity product, adopt 1 as CN 1055934A, the 3-diether compound is that internal electron donor prepares solid catalyst, and adding aluminum alkyls during polymerization again is promotor.EP 0434082A
2Also disclose with 1, the 3-diether compound is the catalyzer of internal electron donor preparation, this patent is with 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal is the catalyzer of internal electron donor preparation, when propylene polymerization, is promotor with the triethyl aluminum, under 70 ℃, 0.7MPa condition, polymerization activity is 15.6 * 10
4Gram pp/ gram Ti, degree of isotacticity is 98.5%.
Adopting ethers is that internal electron donor prepares catalyzer, does not add external electron donor when advantage is polymerization and can obtain high degree of isotacticity product.But ether compound synthetic technology complexity, the corresponding diester class that is higher than of cost.Obtain different degree of isotacticity products, also need select for use different ether compounds to prepare catalyzer, that is to say, the product degree of isotacticity can not be regulated with same catalyzer.
It is a kind of inexpensive and can regulate the efficient polypropylene catalyst of product degree of isotacticity that purpose of the present invention promptly is to provide.
Catalyzer of the present invention is made up of the titanium compound and the internal electron donor compound that are stated from the active magnesium chloride, in catalyst weight, Mg content is 15～25 heavy %, titanium content is 1.0～5.0 heavy %, internal electron donor content is 8～15 heavy %, internal electron donor is the ester of logical formula I and the ether of logical formula II, and the weight ratio of ether and ester is 0.6～2.80
In formula I and (II), R
1～R
4For carbon number 1～10 alkyl, aryl or aralkyl.
The ester of described formula I is preferably o-benzene butyl phthalate ester, 1 of formula II, 3-diether compounds, R wherein
1, R
2Can be the alkyl that carbon number is identical or carbon number is different, be preferably 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
Described titanium compound is selected from halogenated titanium, titan-alkoxide or halogenated alcoholate, as, titanous chloride, titanium tetrachloride, four titanium butoxide, be preferably titanium tetrachloride.
The used active magnesium chloride ball type carrier of catalyzer of the present invention makes with the described method of CN 1109067A.The alcohol amount of containing in this carrier is 1.5～4.0, be preferably 2.0～3.0 moles/mole MgCl
2, its preparation process is as follows:
(1) alcohol closes reaction: the mixture with methyl-silicone oil and whiteruss is a medium, and magnesium chloride and ethanol were reacted 2～4 hours at 110～130 ℃ according to the amount of 2.0～3.0 milliliters of ethanol/gram magnesium chloride.
(2) disperse adducts: alcohol is closed reactant transfer in the mixture medium that is preheated to 110～130 ℃, is made up of methyl-silicone oil and whiteruss, the medium volume is 1.2～2.0 times of alcohol adduct volume, stirs 3～6 minutes with 1500～3000 rev/mins rotating speeds.
(3) chilling solidifies: the adduct emulsion after will disperseing is transferred in advance and is chilled in-15～-30 ℃ the inert solvent medium, and the volume ratio of medium and emulsion is 2～2.5, stirs 20～30 minutes.
(4) Separation and Recovery: treat that above-mentioned mixed system temperature rises to the room temperature after-filtration naturally and goes out solids, the liquid (volume) by 1～1.5 solid (weight) is than wash 3 times vacuum or 50～60 ℃ of nitrogen dryings with inert solvent.
Method for preparing catalyst provided by the invention is as follows:
(1) by the amount of 3.0～6.0 milliliters in every gram carrier the magnesium chloride ball type carrier is mixed with inert solvent, gained suspension is pressed Ti/Mg mol ratio 30～60, preferably 35～45 ratio adds in the compound titanium solution that is chilled to 0～-10 ℃ in advance, slowly be warming up to 60～80 ℃, press magnesium/ether mol ratio 8～22, the ratio of magnesium/ester mol ratio 8～15 adds the ether of formula II and the ester of formula I, the mol ratio of ether and ester is 0.4～1.70,100～125 ℃ were reacted 1.5～4 hours, and filtered while hot is isolated solid particulate.
(2) be that 20～50 ratio is added to solid particulate in the compound titanium solution of preheating according to the Ti/Mg mol ratio, stir and 100～125 ℃ of reactions 1～2 hour, filtered while hot was isolated solid particulate.
(3) with free Cl on 50～70 ℃ the inert solvent flush away particle
-, vacuum or 50～60 ℃ of nitrogen dryings.
Described inert solvent is selected from hexane, heptane, gasoline.
Solid catalyst of the present invention cooperates as catalyst for polymerization of propylene with aluminum alkyls during polymerization, and the aluminum alkyls of selecting for use is preferably triethyl aluminum or triisobutyl aluminium or the mixture of the two, and its consumption is advisable with Al/Ti mol ratio 100～1500.
For obtaining higher degree of isotacticity product, can add external electron donor during polymerization, it is R that external electron donor is selected from general formula
1R
2Si (OR)
2Silicon compound, preferred silicon compound is dimethoxydiphenylsilane or cyclohexyl methyl dimethoxy silane, the consumption of silane is advisable with Al/Si mol ratio 30～40.
The present invention compares with the catalyzer that independent employing two ethers are internal electron donor because employing diether and two ester compounds are that internal electron donor prepares catalyzer, and the consumption of diether has reduced 30～50%, thereby has reduced the catalyzer cost.In addition, use catalyzer of the present invention, not adding external electron donor during polymerization, can to obtain degree of isotacticity be 95% product, add external electron donor during polymerization, the polymkeric substance degree of isotacticity can be heightened 3～4%, make the polymkeric substance degree of isotacticity reach 98.9%, thereby realize that the polymkeric substance degree of isotacticity is adjustable.
Further specify the present invention below by example.
Various analysis test methods are as follows in the example:
Titanium content: spectrophotometry
Mg content: atomic absorption spectrum
Ether content: gas-chromatography
Ester content: gas-chromatography
Example 1～3
Below by preparation catalyzer of the present invention.
(1) method according to CN1109067A prepares ball type carrier.
With 34 gram anhydrous magnesium dichlorides (Fushun Aluminium Works's Industrial products); (Beijing Chemical Plant produces 80 milliliters of dehydrated alcohols; analytical pure) and 100 milliliters of methyl-silicone oils (chemical industry two factories in Beijing produce; chemical pure; viscosity is 300 centipoises); the 100 milliliters of liquid paraffin (chemical plant of seeking talent, Beijing; chemical pure; viscosity is 40 centipoises) under nitrogen protection, join in 500 milliliters of reaction flasks that agitator and prolong are housed; be heated to 120 ℃; react to the magnesium dichloride solid and dissolve fully; shift this solution while hot to methyl-silicone oil and each mixed solution of 150 milliliters of whiteruss; stirred 4 minutes with 2000～3000 rev/mins speed; put into and give in the anhydrous hexane (chemical plant, Yanshan Mountain product, technical grade) that is chilled to-30 ℃, be stirred to system temperature and rise to room temperature; filter; the gained solid is with 200 milliliters of anhydrous hexane 3 times, and vacuum-drying obtains ball type carrier.
(2) Preparation of catalysts
Under nitrogen protection; a certain amount of above-mentioned carrier is suspended in a small amount of anhydrous hexane; add 120 milliliters then and be chilled to (connection chemical reagent factory in Beijing in-10 ℃ the titanium tetrachloride solution in advance; technical grade); stir down and slowly be warming up to 60～80 ℃; add 2 respectively, 2-diisobutyl 1, the 3-Propanal dimethyl acetal (is pressed EP0361493A
1Method synthetic) and diisobutyl phthalate (Beijing chemical reagent work, analytical pure), be warming up to 110 ℃ of reactions 2 hours, filter, solid particulate is put into 50 milliliters of titanium tetrachlorides, 120 ℃ of reactions 1 hour, filtration, solid with anhydrous hexane to there not being Cl
-, making catalyst A～C, feeding quantity and catalyst component content see Table 1 in each catalyst preparation process.
Example 4～6
It below is the propylene polymerization under atmospheric pressure.
500 milliliters of there-necked flasks with high pressure nitrogen-vacuum pump drainage 3 times, are added 300 milliliters of anhydrous hexanes, 0.8M triethyl aluminum and a certain amount of solid catalysts, continue to feed propylene gas at 40 ℃, normal pressure reacted 2 hours down.Behind the reaction terminating, the polymkeric substance drying is weighed, catalyst activity and degree of isotacticity see Table 2.
Example 7
This example is the propylene pressure polymerization.
With 1 liter of autoclave with nitrogen purging after, add 400 milliliters of hexanes successively, 8 milliliters of 0.8M triethyl aluminums, 1.25 the dimethoxydiphenylsilane of milliliter 0.1M, making the Al/Si mol ratio is 35.6, A.70 ℃ add 28 milligrams of solid catalysts again, reaction is 2 hours under the 0.7MPa condition, and catalyst activity and degree of isotacticity see Table 2.
Comparative Examples 1～2
Get the magnesium chloride ball type carrier of 6.7 gram examples 1 preparations, prepare catalyzer a, b by the step of example 1, different is that the internal electron donor compound is 2,2-diisobutyl 1,3-Propanal dimethyl acetal.Carry out propylene polymerization under 40 ℃ then, normal pressure, its active and degree of isotacticity sees Table 2, and each component concentration of catalyzer sees Table 1.
Comparative Examples 3
Get the magnesium chloride ball type carrier of 6.2 gram examples 1 preparations, prepare catalyzer c by the step of example 1, different is that the internal electron donor compound is a diisobutyl phthalate.Getting 30 milligrams of catalyzer c, is promotor with the triethyl aluminum, carries out propylene polymerization under 40 ℃, normal pressure, and polymerization activity and product degree of isotacticity see Table 2, and catalyst component content sees Table 1.
Table 1,2 data show, do internal electron donor with ester separately and prepare solid catalyst, do not add the external electron donor compound during polymerization, polymerization activity and product degree of isotacticity are all lower, do not reach the level of catalyzer of the present invention, do internal electron donor with ether separately and prepare solid catalyst, reach polymerization activity of the present invention and degree of isotacticity, the consumption of ether will increase greatly, if when the consumption of ether is suitable with the present invention, then the product degree of isotacticity significantly descends.In addition, as can be known by table 2 example 4,7 data, when adding the external electron donor compound during polymerization, the product degree of isotacticity can be when not adding external electron donor 95% on transfer to 98.9%, thereby use same solid catalyst, whether the adding of external electron donor regulates the product degree of isotacticity in the time of can be by polymerization.
Table 1
* ether is 2 in the table, 2-diisobutyl 1, and 3-Propanal dimethyl acetal, ester are diisobutyl phthalate.
Table 2
| Instance number | Catalyzer | Polyreaction | Polymerization activity, gram pp/ gram Ti | Degree of isotacticity, % | ||||
| Numbering | Consumption, milligram | Pressure | Triethyl aluminum, consumption, milliliter | DPMS *Consumption, milliliter | Al/Si | |||
| 4 | A | 40.3 | Normal pressure | 6.0 | - | - | 9.5×10 3 | 95 |
| 5 | B | 30.4 | Normal pressure | 8.0 | - | - | 13.4×10 3 | 94.2 |
| 6 | C | 31 | Normal pressure | 5.8 | - | - | 13.0×10 3 | 93.7 |
| 7 | A | 28 | 0.7MPa | 8.0 | 1.8 | 35.6 | 10.0×10 3 | 98.9 |
| Comparative Examples 1 | a | 25 | Normal pressure | 4.2 | - | - | 8.85×10 3 | 94.9 |
| Comparative Examples 2 | b | 36 | Normal pressure | 3.5 | - | - | 16.0×10 3 | 79 |
| Comparative Examples 3 | c | 30 | Normal pressure | 8.0 | - | - | 6.7×10 3 | 86 |
*The DPMS-dimethoxydiphenylsilane
Claims (8)
1. carried polypropylene catalyst, form by the titanium compound and the internal electron donor that are carried on the active magnesium chloride, it is characterized in that by weight Mg content is 15～25 heavy % in the catalyzer, titanium content is 1.0～5.0 heavy %, internal electron donor content is 8～15 heavy %, described internal electron donor is the ester of logical formula I and the ether of logical formula II, and the weight ratio of ether and ester is 0.6～2.80
In logical formula I and (II), R
1～R
4For carbonatoms 1～10 alkyl, aryl or aralkyl.
2. according to the described catalyzer of claim 1, the ester that it is characterized in that formula I is a diisobutyl phthalate.
3. according to claim 1 or 2 described catalyzer, it is characterized in that the ether of formula II is selected from 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
4. according to the described catalyzer of claim 1, it is characterized in that titanium compound is selected from halogenated titanium or titan-alkoxide.
5. according to the described catalyzer of claim 4, it is characterized in that described titanium compound is a titanium tetrachloride.
6. a catalyst for polymerization of propylene comprises described catalyzer of claim 1 and promotor aluminum alkyls, and the Al/Ti mol ratio is 100～1500.
7. according to the described catalyzer of claim 6, it is characterized in that described aluminum alkyls is triethyl aluminum or triisobutyl aluminium, or both mixtures.
8. according to the described catalyzer of claim 6, adding general formula when it is characterized in that chemical polymerization is R
1R
2Si (OR)
2Silicon compound do external electron donor, its Al/Si mol ratio is 30～40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112005A CN1067691C (en) | 1997-05-13 | 1997-05-13 | Carried polypropylene catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112005A CN1067691C (en) | 1997-05-13 | 1997-05-13 | Carried polypropylene catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1199056A CN1199056A (en) | 1998-11-18 |
| CN1067691C true CN1067691C (en) | 2001-06-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112005A Expired - Lifetime CN1067691C (en) | 1997-05-13 | 1997-05-13 | Carried polypropylene catalyst |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153062B (en) * | 2006-09-29 | 2010-09-22 | 中国石油化工股份有限公司 | Olefins polymerizing solid catalyst component, producing method and application of the same |
| WO2018032744A1 (en) | 2016-08-19 | 2018-02-22 | 中国科学院化学研究所 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| CN114605579B (en) * | 2020-12-03 | 2023-07-14 | 万华化学集团股份有限公司 | Polypropylene catalyst, isotactic polypropylene and preparation method thereof |
| CN112625157B (en) * | 2020-12-17 | 2023-04-28 | 黄河三角洲京博化工研究院有限公司 | Catalyst for preparing ultra-pure polypropylene and preparation method for preparing ultra-pure polypropylene by batch bulk method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | Components and catalysts for the polymerization of olefins |
-
1997
- 1997-05-13 CN CN97112005A patent/CN1067691C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | Components and catalysts for the polymerization of olefins |
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| CN1199056A (en) | 1998-11-18 |
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