CN100379771C - Preparation process of catalyst for propylene polymerization - Google Patents
Preparation process of catalyst for propylene polymerization Download PDFInfo
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- CN100379771C CN100379771C CNB200510069078XA CN200510069078A CN100379771C CN 100379771 C CN100379771 C CN 100379771C CN B200510069078X A CNB200510069078X A CN B200510069078XA CN 200510069078 A CN200510069078 A CN 200510069078A CN 100379771 C CN100379771 C CN 100379771C
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Abstract
The present invention discloses a preparation method of a Ziegler. Natta catalyst which can be used for propylene slurry, bodies and a gas-phase polymerization technology. In the process for preparing catalyst of the present invention, solid granules are added as specific treated agents so that the growth process of catalyst particles is controlled, and therefore, the purpose that the modality of propylene polymers and particle size distribution are controlled is obtained. The present invention has the advantages that when the obtained catalyst is used for polymerization, the particle size distribution of more than 96 % of polymers is between 20 meshes and 40 meshes, the stacking density is greater than 0.45 g/ml, and the present invention is very good for industrial production.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that can be used for propylene slurries, body and gas-phase polymerization process, particularly relate to a kind of propylene polymerization Ziegler. the preparation method of Natta catalyst.
Background technology
Ziegler. Natta high-efficient carrier Preparation of catalysts generally is carrier with the magnesium chloride, the carrying transition metal compound.Wherein the most key is the preparing carriers process, because carrier not only plays a part load, dispersed activity center, also has an effect as a kind of particular components and active centre, thereby makes catalyzer have high reactivity.And by the repdocutbility between carrier-catalyst-polymer three, carrier is also being controlled many important indicators such as particle form, size distribution and apparent density of polymkeric substance.The early stage polishing that adopts prepares magnesium chloride support more, but the shortcoming of this method is wayward for the catalyzer process of preparation, and particle form is bad.People also reformed this method afterwards, as US4126576, were that carrier sets out with the titanous chloride, obtained the effective catalyst that high reactivity can be used for gas-phase propylene polymerization by polishing, but the technology relative complex, the cycle is longer.More usual method is to adopt synthetic method to prepare support of the catalyst, is about to magnesium chloride with the alcohol dissolving, separates alcohol by pyrolysis alcohol or chemistry magnesium chloride is separated out again, the titanium component is stated from the magnesium chloride again, forms the active centre.
But because the magnesium chloride crystal formation is very regular survivable, this also just makes separates " modified chlorinated magnesium " the not enough homogeneous that obtains in the process that alcohol separates out magnesium chloride again by pyrolysis alcohol or chemistry, therefore last granules of catalyst broad particle distribution and relatively poor, the easy fragmentation of intensity have been caused, cause when being used for propylene polymerization fine powder content too much, influence the operation of device.Therefore the patent research that has set out with other forms of magnesium compound, " the modified chlorinated magnesium " of preparation homogeneous earlier, then load titanium again obtains size distribution and concentrates and the good catalyzer of intensity, as US5223466.But this method technology is more loaded down with trivial details, and the desired raw material kind is more, makes cost higher.
The invention reside in still and set out by magnesium chloride, the catalyzer synthesis technique is carried out bold innovation, technology is simple, and desired raw material is less.By the developmental process of interpolation particular processing agent control catalyst particle, thereby reach the purpose of controlling propene polymer form and size-grade distribution.
Summary of the invention
Both improve granules of catalyst broad particle distribution and relatively poor, the easy fragmentation of intensity in the prior art for reaching, cause when being used for propylene polymerization fine powder content too much, influence the shortcoming of device operation; Can reach the simplification catalyst preparation process again, reduce the desired raw material kind, the purpose that reduces cost, it is simple to the invention provides a kind of preparation technology, and the desired raw material kind is few, can reach the Ziegler of the purpose of control propene polymer form and size-grade distribution. the preparation method of Natta catalyst.
To describe in detail below according to a kind of Ziegler that can be used for propylene slurries, body and gas-phase polymerization process of the present invention. the preparation method of Natta catalyst.
A. the preparation of magnesium chloride homogeneous phase solution: under nitrogen protection, open and stir, in reactor, add inert solvent, quantitative magnesium chloride and organic alcohol successively; then slowly be warming up to 110～140 ℃; preferred 125～135 ℃, isothermal reaction 0.5～3 hour, preferred 1～2 hour.Add the organic acid anhydride reaction again, continue isothermal reaction 0.5～3 hour, preferred 1～2 hour, stop to stir, obtain homogeneous phase solution, it is standby to lower the temperature.Wherein inert solvent is selected from C
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons; Used organic alcohol is C
1～C
10Straight chain alcohol or isomery alcohol, with the consumption mol ratio of magnesium chloride be 1～8: 1, preferred 2～6: 1; Used organic acid anhydride is various liquid state or SOLID ORGANIC acid anhydrides, with the consumption mol ratio of magnesium chloride be 0.05～1.0: 1, preferred 0.1～0.4: 1.
B. the load of titanium tetrachloride: titanium tetrachloride is joined in the catalyzer synthesis reactor of fully replacing with nitrogen, and titanium tetrachloride is cooled to-30～-15 ℃, preferred-22 ℃, adds magnesium chloride homogeneous phase solution and a certain amount of special processing agent that a process obtains.Wherein, the consumption mol ratio of titanium tetrachloride and magnesium chloride is 10.0～30.0: 1, is preferably 15.0～25.0: 1.This special processing agent is selected from solid granules such as silica gel, aluminum oxide, granules of catalyst, magnesium oxide, magnesium chloride; grain diameter is at 0.1～10.0 μ m; be preferably 0.5～3.0 μ m; 1.0～2.0 μ m more preferably; 1.5 μ m most preferably; solid granule high temperature dehydration deoxidation under 100～800 ℃ of nitrogen protections, with the consumption mass ratio of magnesium chloride be 0.00001～0.001: 1, be preferably 0.0001～0.0004: 1.The addition sequence of magnesium chloride homogeneous phase solution and special processing agent can be any.Pass through the temperature programming stage again, promptly-22 ℃ of constant temperature 1～6 hour,-22 ℃～20 ℃, constant temperature 1～6 hour, 20 ℃～pyroreaction temperature, constant temperature 2～6 hours, the pyroreaction temperature is controlled between 100 ℃～140 ℃, constant temperature 1～4 hour when the pyroreaction temperature again, add multi-carboxylate's reaction therein and obtain solid particulate, the multi-carboxylate is selected from aliphatics multi-carboxylate or aromatic series multi-carboxylate etc., specifically is selected from: diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diisobutyl phthalate, n-butyl phthalate, diethyl phthalate, dipropyl phthalate, diamyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, triethyl trimellitate, tributyl trimellitate etc.Preferably: diisobutyl phthalate, n-butyl phthalate.The consumption mol ratio of multi-carboxylate and magnesium chloride is 2～10: 1, is preferably 4～6: 1, and the multi-carboxylate adds in the time of 40～100 ℃.Behind the constant temperature, the filtrate press filtration in the reactor in returnable bottle, is then added a certain amount of fresh titanium tetrachloride again, heat up rapidly, constant temperature is 1～4 hour then, and preferred 2 hours, temperature of reaction was 100 ℃～140 ℃.The multi-carboxylate can repeatedly react with titanium tetrachloride, preferred 2～4 times.
C. the washing drying of catalyzer: the filtrate press filtration in the reactor in returnable bottle, is repeatedly washed solid particulate with inert solvent, obtain catalyst prod through vacuum-drying again.Wherein inert solvent is identical with step a, and consumption is 5～20ml/g magnesium chloride, 2～20 hours time of drying, 40～80 ℃ of temperature.
Solid catalyst of the present invention cooperates as the propylene polymerization catalyzer with aluminum alkyls.The aluminum alkyls of selecting for use is preferably triethyl aluminum or triisobutyl aluminium or the mixture of the two, and its consumption is with aluminium/titanium mol ratio 100～1000: 1 is advisable.
For obtaining more high normal 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 second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, cyclohexyl methyl dimethoxy silane (C-DONOR), dicyclopentyl dimethoxyl silane (D-DONOR) etc.The consumption of silane is with aluminium/silicon mol ratio 8～40: 1 is advisable.
When the resulting catalyzer of the present invention is used for propylene polymerization, be applicable to propylene slurries, body and gas-phase polymerization process, this technology comprises to be made the propylene homopolymerization or makes propylene and ethene or other comonomer copolymerization.
The Ziegler that can be used for propylene slurries, body and gas-phase polymerization process provided by the invention. the preparation method of Natta catalyst, by in catalyst preparation process, adding a kind of special processing agent, the developmental process of control catalyst particle, thus reach the purpose of controlling propene polymer form and size-grade distribution.When resulting catalyzer was used for polymerization, the polymkeric substance of size-grade distribution between 20～40 orders can reach more than 96%, and tap density is very beneficial for industrial production greater than 0.45g/ml.
Following table is for the catalyzer (sample A) that adds the special processing agent and make and do not add the polymerization evaluation result contrast of the catalyzer (sample B) that the special processing agent makes.It is higher that sample A carries out the polyacrylic packing density of particle that polyreaction obtains, and particle size distribution is more concentrated.
Annotate: mass polymerization, 70 ℃, 2hr, 3.0MPa, H
2Pressure 0.2MPa, AT: Ti: Si=500: 1: 40
Embodiment
Embodiment 1
The preparation ingredient of solid catalyst
Under nitrogen protection, open and stir, in reactor, add 40ml decane, 7g magnesium chloride and 30ml isooctyl alcohol successively, then slowly be warming up to 130 ℃, isothermal reaction 2 hours.Add the 1.7g phthalic anhydride again, continued isothermal reaction 2 hours, stop to stir, it is standby to reduce to room temperature naturally.
The 200ml titanium tetrachloride is joined in the catalyzer synthesis reactor of fully replacing with nitrogen, be cooled to-22 ℃, magnesium chloride homogeneous phase solution under the room temperature that makes was splashed into wherein in 1 hour, in the dropping process, keep temperature in the kettle at-22 ± 1 ℃, after being added dropwise to complete, the silica gel that adds 3mg median size 1.5 μ m, constant temperature 1 hour slowly was warming up to 108 ℃ in 4 hours, add the diisobutyl phthalate of 5.0ml when temperature is 90 ℃, continue to be warming up to 113 ℃, constant temperature 2 hours.Constant temperature in returnable bottle, then adds the filtrate press filtration in the reactor the fresher titanium tetrachloride of 200ml and is warming up to 115 ℃ rapidly, constant temperature 2 hours after finishing.
Filtrate press filtration in the reactor in returnable bottle, is used the resulting solid catalyst of hexane wash five times, each hexane consumption 150ml.Vacuumize drying at last, obtain catalyzer dry powder.
Ti (weight %) is 2.71%.
Liquid phase bulk propylene polymerization.
After the autoclave that 4 liters of bands are stirred is fully replaced with propylene, add 0.8M triethyl aluminum, a certain amount of solid catalyst, 0.2M dimethoxydiphenylsilane successively, (add-on of hydrogen is: the pressure drop of the hydrogen gas tank 0.2MPa of 100ml) to add 1.5 kilograms of liquid propenes and hydrogen again, with still temperature rise to 70 ℃, reacted 2 hours, after the taking-up solid polypropylene is carried out drying, weighing, calculate catalyst activity, and measure tap density, degree of isotacticity and the size-grade distribution of polymkeric substance.Concrete data see Table 1.
Embodiment 2
Prepare catalyst component with the method identical, but when the preparation catalyst component, add silica gel earlier with embodiment 1, after add the magnesium chloride homogeneous phase solution, the median size of adding is that the silica gel of 1.5 μ m changes 1mg into by 3mg.Ti (weight %) is 2.55%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 3
Prepare catalyst component with the method identical with embodiment 1, but when the preparation catalyst component, the silica gel of the median size 1.5 μ m of adding changes 4mg into by 3mg, multi-carboxylate's diisobutyl phthalate changes n-butyl phthalate into.Ti (weight %) is 2.86%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 4
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel that adds median size 1.5 μ m changes the granules of catalyst of median size 1.0 μ m, consumption 0.5mg into embodiment 1.Ti (weight %) is 2.82%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 5
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel that adds median size 1.5 μ m changes the magnesium oxide of median size 2.0 μ m, consumption 6mg into embodiment 1.Ti (weight %) is 2.69%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 6
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel that adds median size 1.5 μ m changes the magnesium chloride granules of median size 0.5 μ m, consumption 8mg into embodiment 1.Ti (weight %) is 2.62%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 7
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel that adds median size 1.5 μ m changes the alumina particle of median size 3.0 μ m, consumption 9mg into embodiment 1.Ti (weight %) is 2.52%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Embodiment 8
Prepare catalyst component with the method identical, but when the preparation catalyst component, the silica gel that adds median size 1.5 μ m changes the alumina particle of median size 6.0 μ m, consumption 10mg into embodiment 1.Ti (weight %) is 2.50%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Comparative example 1
Prepare catalyst component with the method identical, but when the preparation catalyst component, do not add silica gel with embodiment 1.Ti (weight %) is 2.89%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
Table 1
Annotate: mass polymerization, 70 ℃, 2hr, 3.0MPa, H
2Pressure 0.2MPa, AT: Ti: Si=500: 1: 40
Claims (7)
1. propylene polymerization Preparation of catalysts method is characterized in that: add a kind of as the special processing agent in the solid granule of silica gel, aluminum oxide, magnesium oxide, magnesium chloride in catalyst preparation process, this method may further comprise the steps:
A. the preparation of magnesium chloride homogeneous phase solution: under nitrogen protection, in the presence of inert solvent, quantitatively magnesium chloride successively reacts with organic alcohol and organic acid anhydride, the consumption mol ratio of organic alcohol and magnesium chloride is 1～8: 1, the consumption mol ratio of organic acid anhydride and magnesium chloride is 0.05～1.0: 1,110～140 ℃ of temperature of reaction, constant temperature time 1～6 hour, obtain homogeneous phase solution, it is standby to lower the temperature;
B. the load of titanium tetrachloride: under nitrogen protection, titanium tetrachloride is cooled to-30～-15 ℃, add the magnesium chloride homogeneous phase solution that a process obtains, the consumption mol ratio of titanium tetrachloride and magnesium chloride is 10.0～30.0: 1, and a kind of silica gel that is selected from, aluminum oxide, magnesium oxide, the solid granule of magnesium chloride is as the special processing agent, grain diameter is at 0.1～10.0 μ m, high temperature dehydration deoxidation under 100～800 ℃ of nitrogen protections, with the consumption mass ratio of magnesium chloride be 0.00001～0.001: 1, through the temperature programming stage :-22 ℃ of constant temperature 1～6 hour,-22 ℃～20 ℃, constant temperature 1～6 hour, 20 ℃～pyroreaction temperature, constant temperature 2～6 hours, the pyroreaction temperature is 100 ℃～140 ℃, again constant temperature 1～4 hour when 100 ℃～140 ℃ of pyroreaction temperature; Add multi-carboxylate's reaction therein and obtain solid particulate, the consumption mol ratio of multi-carboxylate and magnesium chloride is 2～10: 1, and the multi-carboxylate adds in the time of 40～100 ℃; Reaction gained solids is handled 1～3 time 100 ℃～140 ℃ of temperature of reaction, 1～4 hour time again with fresh titanium tetrachloride;
C. the washing drying of catalyzer is washed solid particulate with inert solvent, obtains catalyst prod through vacuum-drying again.
2. according to the process of claim 1 wherein: the inert solvent described in the step a is selected from C
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons; Used organic alcohol is C
1～C
10Straight chain alcohol or isomery alcohol, used organic acid anhydride are liquid state or SOLID ORGANIC acid anhydrides.
3. according to the process of claim 1 wherein: the consumption mol ratio of used alcohol and magnesium chloride is 2～6: 1 among the step a; The consumption mol ratio of used organic acid anhydride and magnesium chloride is 0.1～0.4: 1; 125～135 ℃ of temperature of reaction, constant temperature time 2～4 hours.
4. according to the process of claim 1 wherein, the titanium tetrachloride cooling temperature described in the step b is-22 ℃; The consumption mol ratio of titanium tetrachloride and magnesium chloride is 15.0～25.0: 1; Special processing agent solid grain size is 0.5～3.0 μ m, and the consumption mass ratio of solid granule and magnesium chloride is 0.0001～0.0004: 1; The multi-carboxylate is selected from aliphatics multi-carboxylate or aromatic series multi-carboxylate, and the consumption mol ratio of multi-carboxylate and magnesium chloride is 4～6: 1.
5. according to the process of claim 1 wherein, the special processing agent solid grain size described in the step b is 1～2 μ m; The multi-carboxylate is selected from: diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diisobutyl phthalate, n-butyl phthalate, diethyl phthalate, dipropyl phthalate, diamyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, triethyl trimellitate, tributyl trimellitate.
6. according to the process of claim 1 wherein, the special processing agent solid grain size described in the step b is 1.5 μ m; The multi-carboxylate is selected from: diisobutyl phthalate, n-butyl phthalate.
7. according to the process of claim 1 wherein, the inert solvent described in the step c is identical with step a, and consumption is 5～20ml/g magnesium chloride, and dry 2～20 hours, 40～80 ℃ of temperature.
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| CNB200510069078XA CN100379771C (en) | 2005-05-11 | 2005-05-11 | Preparation process of catalyst for propylene polymerization |
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| CN100379771C true CN100379771C (en) | 2008-04-09 |
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| CN110467694B (en) * | 2018-05-09 | 2022-01-04 | 中国石油天然气股份有限公司 | Preparation method of composite carrier of propylene high-temperature polymerization catalyst, propylene high-temperature polymerization catalyst component and propylene high-temperature polymerization catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126576A (en) * | 1974-12-06 | 1978-11-21 | Toho Titanium Company, Limited | Process for preparation of catalytic components for polymerization of α-olefins |
| US5223466A (en) * | 1992-03-20 | 1993-06-29 | Amoco Corporation | Olefin polymerization and copolymerization catalyst |
| CN1410457A (en) * | 2002-11-08 | 2003-04-16 | 营口市向阳催化剂有限责任公司 | Preparation method of solid titanium catalyst component used for olefine polymerization |
| CN1532210A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyt and its component for polymerization of ethylene |
-
2005
- 2005-05-11 CN CNB200510069078XA patent/CN100379771C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126576A (en) * | 1974-12-06 | 1978-11-21 | Toho Titanium Company, Limited | Process for preparation of catalytic components for polymerization of α-olefins |
| US5223466A (en) * | 1992-03-20 | 1993-06-29 | Amoco Corporation | Olefin polymerization and copolymerization catalyst |
| CN1410457A (en) * | 2002-11-08 | 2003-04-16 | 营口市向阳催化剂有限责任公司 | Preparation method of solid titanium catalyst component used for olefine polymerization |
| CN1532210A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyt and its component for polymerization of ethylene |
Non-Patent Citations (1)
| Title |
|---|
| 用调节剂改善聚丙烯高效催化剂性能的研究. 张文平，黄庆军，石勤智，汪洁，景振华.现代化工，第23卷. 2003 * |
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