CN1506384A - Prepn process of polypropylene catalyst - Google Patents
Prepn process of polypropylene catalyst Download PDFInfo
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- CN1506384A CN1506384A CNA021555567A CN02155556A CN1506384A CN 1506384 A CN1506384 A CN 1506384A CN A021555567 A CNA021555567 A CN A021555567A CN 02155556 A CN02155556 A CN 02155556A CN 1506384 A CN1506384 A CN 1506384A
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Abstract
The present invention features applying ultrasonic technology in the preparation process of polypropylene catalyst. The preparation process includes the following steps: mixing anhydrous MgCl2, organic alcohol and inert solvent, inserting ultrasonic probe into the reactor, heating to 120-150 deg.c, turning on the ultrasonic unit while tuning the ultrasonic wave frequency to 20-50 KHz, adding phenyl anhydride and organic silicide and reaction for 1-5 hr to obtain alcoholate; adding the alcoholate cooled to room temperature into titanium compound solution cooled to -40 deg.c to -15 deg.c, heating to 90-110 deg.c, adding ester and reaction at 100-130 deg.c for 1-3 hr, and filtering to separate out solid catalyst grain. Applying ultrasonic wave technology in preparing polypropylene catalyst can raise the polymerizing activity of the catalyst and the bulk density of the polymer.
Description
Technical field: the present invention is a kind of polypropylene catalyst preparation method, particularly the supported solid Preparation of catalysts method used of propylene polymerization.
Background technology: from the Z-N invention fifties in last century polyolefin catalyst so far, such polyolefin catalyst has obtained fast development, and the Preparation of catalysts method is also progressively enriched and be perfect.Mainly be to prepare polyolefin catalyst at present both at home and abroad with chemical reaction method, this type of catalyzer mainly is made up of the titanium compound and the internal electron donor compound that are carried on the active magnesium chloride, internal electron donor can be the ester class, compounds such as ethers, as publication number is CN1345886A, denomination of invention is " a high-effective carrier catalyst for polymerizing olefines; it is stated from the magnesium chloride support with the aluminum alkyls reaction product by the halogen titanium compound forms; it is characterized by by alcohol and magnesium chloride; ester; the synthetic magnesium chloride alcohol adduct that contains ester in phthalic anhydride and the solvent oil; at low temperatures, the halogen titanium compound reacts with aluminum alkyls earlier, then with the magnesium chloride alcohol adduct reaction that contains ester, heat up, add ether and the polynary ester of organic acid, after filtration, washing obtains catalyzer; And for example notification number is CN1067691C, the day for announcing is a kind of carried polypropylene catalyst in June 27 calendar year 2001, and it is made up of the titanium and the internal electron donor compound that are carried on the active magnesium chloride, and internal electron donor is ester and ether, these methods are general polyolefin catalyst preparation method
Be not limited thereto in the prior art.
Document shows, sound is as a kind of energy input mode, can influence chemical reaction, sound has broad application prospects at aspects such as catalyzer manufacturing, organic synthesis, molecular degradation and polymerization, heat and mass transports, ultrasonic technology is used for the polyolefin catalyst preparation process, does not also find in the prior art.
Summary of the invention: purpose of the present invention promptly is to provide a kind of polypropylene catalyst preparation method, and ultrasonic technology is used for the polypropylene catalyst preparation process, to improve polypropylene catalyst polymerization activity and polymer stacks density.
The polypropylene catalyst preparation comprises the following steps:
(1) under protection of inert gas; Magnesium Chloride Anhydrous is mixed with inert solvent by 2～5 mol ratios with organic alcohol; and with in the ultrasonic probe insertion reaction device; be warming up to 120 ℃～150 ℃; open ultrasonic wave, and ultrasonic frequency is adjusted into 20～50KHz, optimum value is 23.5kHz; ratio in magnesium/acid anhydride mol ratio 5～10, magnesium/silicon mol ratio 20～50 adds phthalic anhydride and a kind of silicoorganic compound that are selected from formula (II)-(IV), reacts to obtain alcohol adduct in 1～5 hour.
(2). the alcohol adduct that will be chilled to room temperature according to the ratio of titanium/magnesium mol ratio 20～50 joins in advance in the compound titanium solution that is chilled to-15 ℃～-40 ℃, be warming up to 90 ℃～110 ℃, ratio according to magnesium/ester mol ratio 2～10 adds a kind of ester that is selected from formula (I), 100 ℃～130 ℃ reactions 1～3 hour, filter to isolate solid particle catalyst.
(3). the ratio according to titanium/magnesium mol ratio 20～50 joins solid particulate in the compound titanium solution, stirs and 100 ℃～130 ℃ reactions 1.5～3 hours, filters to isolate solid particle catalyst.
(4). the inert solvent washing solid particulate with 50 ℃～80 ℃ had both obtained solid particle catalyst after the drying.
It is 2～8 monohydroxy-alcohol that described organic alcohol is selected from carbon atom number.
Described inert solvent is selected from hexane, heptane, decane.
The internal electron donor compound is the ester of general formula (I) and a kind of silicoorganic compound that are selected from general formula (II)-(IV).
R
9Si(OR
10)
3??????????(III)
R
11R
12Si(OR
13)
2?????(IV)
In the general formula (I)-(IV), R
1～R
13For carbonatoms is that alkyl, the carbonatoms of 1-10 is the 6-10 aryl or aralkyl.
During preparation, the ester class is generally elected n-butyl phthalate, diisobutyl phthalate or dimixo-octyl phthalate as, is preferably diisobutyl phthalate.
Silicoorganic compound are preferably tetraethoxysilane.
Titanium compound is halogenated titanium or titan-alkoxide, is preferably titanous chloride, titanium tetrachloride, four titanium butoxide, most preferably is titanium tetrachloride.
Catalyzer with polypropylene catalyst preparation method of the present invention makes can cooperate 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 advisable with aluminium/titanium mol ratio 100～1000.In addition, for obtaining the product of suitable degree of isotacticity, can add external electron donor during polymerization.It is R that external electron donor is selected from general formula
11R
12Si (OR
13)
2Silicoorganic compound, preferred silicon compound is dimethoxydiphenylsilane or cyclohexyl methyl dimethoxy silane, the consumption of silane is advisable with aluminium/silicon mol ratio 20～40.
Ultrasonic wave is acted on the polypropylene catalyst preparation process, ultrasonic cavitation effect and the mechanical effect of utilizing ultrasonic wave in catalyzer, to propagate, can make catalyst particle become closely knit, reach the ideal size-grade distribution, and can improve polymerization catalyst activity and polymer stacks density.
Use ultrasonic wave in step (1), can improve the average activity and the bulk density of catalyzer, and the change of polymkeric substance particle diameter is big, size-grade distribution is more concentrated, has improved the over-all properties of polypropylene catalyst greatly.Also can use ultrasonic wave in step (2) building-up process, though catalyst activity is not improved, even some descends, and the bulk density of polymkeric substance has raising, and on size-grade distribution, polymer particle is more in the 40-80 purpose.In addition, in building-up process, use ultrasonic wave, can improve catalyst Ti content.
Embodiment:
Further specify the present invention below by embodiment.
Embodiment 1～3
Under nitrogen protection; 6 gram Magnesium Chloride Anhydrouss, 24 gram isooctyl alcohol and 22 gram decane are joined in 500 milliliters of reactors that agitator is housed; and with in the ultrasonic probe insertion reaction device; be heated to 130 ℃; open ultrasonic wave; and the adjustment ultrasonic frequency is followed successively by 23.5kHz, 21kHz and 35kHz; reacted 2 hours; this moment, magnesium chloride dissolved fully; the tetraethoxysilane that adds 1.4 gram phthalic anhydrides and 2.5 mmoles is as the interior electron compound of giving; continue to react to phthalic anhydride and dissolve fully, obtain alcohol adduct, it is standby that alcohol adduct is chilled to room temperature.
Under nitrogen protection; above-mentioned alcohol adduct is joined in advance in 150 milliliters of titanium tetrachloride solutions that are chilled to-21 ℃; stir down and slowly be warming up to 100 ℃, add the internal electron donor diisobutyl phthalate, be warming up to 120 ℃ of reactions 2 hours; filter; solid particulate is put into 100 milliliters of titanium tetrachloride solutions, and 120 ℃ were reacted 1 hour, filtered; divide the washing solid particulate 4 times with anhydrous hexane, make catalyst A～C.
Example 4～5
Under nitrogen protection; 6 gram Magnesium Chloride Anhydrouss, 24 gram isooctyl alcohol and 22 gram decane are joined in 500 milliliters of reactors that agitator is housed; be heated to 130 ℃; react to magnesium chloride and dissolve fully; the tetraethoxysilane that adds 1.4 gram phthalic anhydrides and 2.5 mmoles; continue to react to phthalic anhydride and dissolve fully, obtain alcohol adduct.It is standby that alcohol adduct is chilled to room temperature.
Under nitrogen protection; above-mentioned alcohol adduct is joined in advance in 150 milliliters of titanium tetrachloride solutions that are chilled to-21 ℃; and with in the ultrasonic probe insertion reaction device; open ultrasonic wave; and the adjustment ultrasonic frequency is followed successively by 23.5kHz and 35KHz; stir down and slowly be warming up to 100 ℃; add diisobutyl phthalate, be warming up to 120 ℃ of reactions 2 hours, stop ultrasonic wave; filter; solid particulate is put into 100 milliliters of titanium tetrachloride solutions, and 120 ℃ were reacted 1 hour, filtered; divide several to wash solid particulate with anhydrous hexane, make catalyzer D～E.
Example 6～10
It below is the propylene slurry polymerization.
After the autoclave that 4 liters of bands are stirred is fully replaced with propylene, press aluminium, titanium, silicon mol ratio is that 500: 1: 20 ratio adds triethyl aluminum successively, the solid catalyst sample, cyclohexyl methyl dimethoxy silane, add 1600 milliliters of hexanes again, the hydrogen (hydrogen gas tank of 100ml) that adds the 0.4MPa pressure drop, heat to autoclave, and feeding gaseous propylene, with still temperature rise to 70 ℃, ask that the open close still of keeping of going into gaseous propylene is pressed in 0.7MPa reaction 2 hours, the cooling back is taken out solid polypropylene and is carried out drying, after the weighing, calculate catalyst activity, and measure the tap density of polymkeric substance, degree of isotacticity and size-grade distribution.Concrete data see Table 1.
Comparative Examples 1
Step by embodiment 1 prepares catalyzer a, and different is not use ultrasonic wave in preparation process.Carry out the propylene slurry polymerization by the step of example 6 then.Concrete data see Table 1.
Table 1 data show, close at alcohol and to use ultrasonic wave in the process, the average activity of catalyzer can improve more than 10%, the bulk density of polymkeric substance also can improve about 10%, and polymer particle in 20-40 purpose part substantially greater than 90%, illustrate that the polymkeric substance particle diameter becomes big, size-grade distribution is more concentrated, and this just is equivalent to improve greatly the over-all properties of polypropylene catalyst.Use ultrasonic wave in building-up process, catalyst activity is not improved, even some decline, but the bulk density of polymkeric substance has raising, and on size-grade distribution, polymer particle is more in the 40-80 purpose.In addition, in building-up process, use ultrasonic wave, can improve catalyst Ti content.
Table 1
| Instance number | Catalyzer | Polymerization activity gpp/gcat | The PP bulk density, g/ml | PP sieves (order) % | ||||
| Numbering | Titanium content | ??＞20 | ??20-40 | ??40-80 | ??＜80 | |||
| ????1 | ??A | ???1.84 | ?13200 | ?0.42 | ??4.4 | ??82.3 | ??11.1 | ??2.2 |
| ????2 | ??B | ???1.86 | ?12500 | ?0.42 | ??1.4 | ??93.1 | ??4.0 | ??1.5 |
| ????3 | ??C | ???1.96 | ?12000 | ?0.40 | ??1.0 | ??94.0 | ??3.6 | ??1.4 |
| ????4 | ??D | ???3.96 | ?9800 | ?0.41 | ??2.2 | ??31.4 | ??59.5 | ??6.9 |
| ????5 | ??E | ???4.69 | ?6400 | ?0.42 | ??1.3 | ??8.2 | ??50.3 | ??40.2 |
| Comparative Examples 1 | ??a | ???2.30 | ?11500 | ?0.38 | ??0.6 | ??15.1 | ??69.8 | ??14.5 |
PP: polypropylene
Claims (3)
1, a kind of polypropylene catalyst preparation method is characterized in that ultrasonic technology is used for the polypropylene catalyst preparation process, and its method comprises the following steps:
(1) under protection of inert gas; Magnesium Chloride Anhydrous is mixed with inert solvent by 2～5 mol ratios with organic alcohol; and with in the ultrasonic probe insertion reaction device; be warming up to 120 ℃～150 ℃; open ultrasonic wave; and ultrasonic frequency is adjusted into 20～50KHz, and add phthalic anhydride and a kind of silicoorganic compound that are selected from formula (II)-(IV) as the internal electron donor compound in the ratio of magnesium/acid anhydride mol ratio 5～10, magnesium/silicon mol ratio 20～50, react and obtained alcohol adduct in 1～5 hour.
(2). the alcohol adduct that will be chilled to room temperature according to the ratio of titanium/magnesium mol ratio 20～50 joins in advance in the compound titanium solution that is chilled to-15 ℃～-40 ℃, be warming up to 90 ℃～110 ℃, ratio according to magnesium/ester mol ratio 2～10 adds a kind of ester of formula (I) that is selected from as the internal electron donor compound, 100 ℃～130 ℃ reactions 1～3 hour, filter to isolate solid particle catalyst.
(3). the ratio according to titanium/magnesium mol ratio 20～50 joins solid particulate in the compound titanium solution, stirs and 100 ℃～130 ℃ reactions 1.5～3 hours, filters to isolate solid particle catalyst.
(4). the inert solvent washing solid particulate with 50 ℃～80 ℃ had both obtained solid particle catalyst after the drying.
Its formula of (I)-(IV) is
R
9Si(OR
10)
3?????????????(III)
R
11R
12Si(OR
13)
2????????(IV)
In the general formula (I)-(IV), R
1～R
13For carbonatoms is that alkyl, the carbonatoms of 1-10 is the 6-10 aryl or aralkyl.
2. according to the described preparation method of claim 1, it is characterized in that described frequency of ultrasonic is 23.5kHz.
3. according to the described preparation method of claim 1, it is characterized in that described organic alcohol is that carbon atom number is 2～8 monohydroxy-alcohol; Described inert solvent is hexane, heptane or decane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155556 CN1216920C (en) | 2002-12-11 | 2002-12-11 | Prepn process of polypropylene catalyst |
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|---|---|---|---|
| CN 02155556 CN1216920C (en) | 2002-12-11 | 2002-12-11 | Prepn process of polypropylene catalyst |
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| CN1216920C CN1216920C (en) | 2005-08-31 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422226C (en) * | 2005-05-12 | 2008-10-01 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| WO2011131033A1 (en) | 2010-04-22 | 2011-10-27 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst comprising same |
| WO2012019438A1 (en) | 2010-08-12 | 2012-02-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst thereof |
| CN102863564A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
| CN102863563A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Ultrahigh molecular polyethylene catalyst and preparation method |
| WO2015043526A1 (en) | 2013-09-30 | 2015-04-02 | 中国石油化工股份有限公司 | Catalyst composition for olefin polymerization and application of same |
| CN106496373A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN106589176A (en) * | 2016-12-20 | 2017-04-26 | 大唐国际化工技术研究院有限公司 | Polyolefin catalyst and preparation method and application thereof |
| WO2021018042A1 (en) | 2019-07-26 | 2021-02-04 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and use thereof |
| CN112409514A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
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- 2002-12-11 CN CN 02155556 patent/CN1216920C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100422226C (en) * | 2005-05-12 | 2008-10-01 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| WO2011131033A1 (en) | 2010-04-22 | 2011-10-27 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst comprising same |
| WO2012019438A1 (en) | 2010-08-12 | 2012-02-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst thereof |
| CN102863564A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
| CN102863563A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Ultrahigh molecular polyethylene catalyst and preparation method |
| CN102863564B (en) * | 2011-07-04 | 2014-12-10 | 中国石油化工股份有限公司 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
| CN102863563B (en) * | 2011-07-04 | 2014-12-10 | 中国石油化工股份有限公司 | Ultrahigh molecular polyethylene catalyst and preparation method |
| US9822196B2 (en) | 2013-09-30 | 2017-11-21 | China Petroleum & Chemical Corporation | Catalyst composition for olefin polymerization and application of same |
| WO2015043526A1 (en) | 2013-09-30 | 2015-04-02 | 中国石油化工股份有限公司 | Catalyst composition for olefin polymerization and application of same |
| CN106496373A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN106496373B (en) * | 2015-09-08 | 2019-09-27 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN106589176A (en) * | 2016-12-20 | 2017-04-26 | 大唐国际化工技术研究院有限公司 | Polyolefin catalyst and preparation method and application thereof |
| CN106589176B (en) * | 2016-12-20 | 2019-10-25 | 大唐国际化工技术研究院有限公司 | A kind of polyolefin catalyst and its preparation method and application |
| WO2021018042A1 (en) | 2019-07-26 | 2021-02-04 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and use thereof |
| US11840508B2 (en) | 2019-07-26 | 2023-12-12 | China Petroleum & Chemical Corporation | Catalyst system for olefin polymerization and use thereof |
| CN112409514A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
| CN112409514B (en) * | 2019-08-23 | 2023-04-28 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
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| CN1216920C (en) | 2005-08-31 |
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