CN1861650A - Preparation process of catalyst for ethylene polymerization - Google Patents
Preparation process of catalyst for ethylene polymerization Download PDFInfo
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- CN1861650A CN1861650A CN 200510069149 CN200510069149A CN1861650A CN 1861650 A CN1861650 A CN 1861650A CN 200510069149 CN200510069149 CN 200510069149 CN 200510069149 A CN200510069149 A CN 200510069149A CN 1861650 A CN1861650 A CN 1861650A
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Abstract
A process for preparing a Ziegler-Natta catalyst used for the sludge polymerization of ethene features that in its preparing procedure the ultrasonic wave technique is used for increasing the content of Ti and improving the granularity distribution of polymer.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for ethylene polymerization, particularly ethylene polymerization supported solid Preparation of catalysts method.
Background technology
Document shows that sound can influence chemical reaction as a kind of energy input mode, and sound has wide practical use at aspects such as catalyzer manufacturing, organic synthesis, molecular degradation and polymerization, heat and mass transports.JP76 127185 is traditional polyethylene catalysts preparation methods, 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.
CN1506384A is used for the preparation process of polypropylene catalyst with ultrasonic technology, has obtained good effect, but in existing document with ultrasonic applications in the preparation process of polyethylene catalysts, discovery is not also arranged.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyethylene catalysts, by ultrasonic technology being used for the preparation process of polyethylene catalysts, with titanium content that improves catalyzer and the size distribution of improving polymkeric substance.
Method for preparing catalyst provided by the invention is as follows:
1) under nitrogen protection, inert solvent and quantitative organic ester are joined in the catalyzer synthesis reactor, stir under the room temperature.Described organic ester is selected from four titan-alkoxides, and is preferred: tetramethoxy titanium, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide etc.
Adding magnesium chloride again, is 0.01～0.5: 1 adding by ester magnesium mol ratio, slowly is warming up to 50～70 ℃, keeps reaction 1～2 hour, and preferable reaction temperature is 60 ℃, preferred 1 hour of reaction times.Then slowly drip one or more organic alcohol, by the magnesium alkoxide mol ratio is 0.2～2.0: 1 adding, described organic alcohol is as alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, isohexyl alcohol, or their mixture.Keep 50～70 ℃ of temperature in the kettle, keep reaction 1～2 hour, preferred 600 ℃ of temperature, preferred 1 hour of constant temperature time.Open the ultrasonic wave 20～50KHZ that adjusts frequency, preferred 30～40KHZ, most preferably 35 ± 1KHZ keeps reaction 15～90 minutes, and preferred 30～60 minutes, most preferably 60 minutes.And keep 50～70 ℃ of temperature in the kettle, preferred 60 ℃.
2) stop ultrasonic wave, in 30～45 minutes, be slowly to splash into synthesis reactor at 0.05～1.0: 1 by titanium magnesium mol ratio with quantitative titanium tetrachloride, again open ultrasonic wave, 20～50KHZ adjusts frequency, preferred 30～40KHZ, most preferably 35 ± 1KHZ keeps reaction 15-90 minute, preferred 30～60 minutes, most preferably 60 minutes.Close ultrasonic wave, isothermal reaction 1～2 hour, preferred 1 hour of constant temperature time.Twice ultrasonic wave can be chosen wantonly once, also can all open for twice, opens to good with two.
3) stop stirring, with upper strata mother liquor sucking-off, wash solid particulate with inert solvent, drying makes catalyzer, and preferred drying temperature is 50～70 ℃.
Inert solvent described in each step is selected from C
5～C
15Alkane, be excellent with hexane.
The catalyzer that makes with polyethylene catalysts preparation method of the present invention, can be used from that ethylene homo closes with organoaluminum promotor one, ethene and alpha-olefin copolymer, the organoaluminum promotor is an alkylaluminium cpd, its consumption is excellent with AL/Ti mol ratio 50～1000: 1, and with 50～200: 1 is optimum.
The preparation method who can be used for the ziegler natta catalyst of ethylene thick liquid polymerizing provided by the invention by use the ultrasonication technology in catalyst preparation process, improves the titanium content of polyethylene catalysts, and improves the size-grade distribution of polymkeric substance effectively.The catalyzer distinguishing feature of using this technology preparation is that the polyethylene particle size-grade distribution of polymerization gained is concentrated, even, mainly is distributed between 20～40 orders, is very beneficial for industrial production.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
Preparation of Catalyst:
Four titanium butoxide with 400ml hexane and 5ml under nitrogen protection join in the catalyzer synthesis reactor, stir 10 minutes under the room temperature.Add the 10g magnesium chloride again, slowly be warming up to 60 ℃, keep reaction 60 minutes; Then slowly drip the propyl carbinol of 4ml, keep 60 ℃ of temperature in the kettle, constant temperature 60 minutes.
Open the ultrasonic wave 35 ± 1KHZ that adjusts frequency, keep reaction 60 minutes, and keep 60 ℃ of temperature in the kettle.
Stop ultrasonic wave, in 30～45 minutes the 15ml titanium tetrachloride is added dropwise in the synthesis reactor, open ultrasonic wave again, the 35 ± 1KHZ that adjusts frequency keeps reaction 60 minutes, closes ultrasonic wave, isothermal reaction 60 minutes;
Stop stirring,, use hexane wash upper strata mother liquor sucking-off.Under 60 ℃, carry out drying 15 minutes, and made this catalyzer.
Ti (weight %) is 5.21%.
Ethylene polymerization:
Nitrogen pump drainage three times of 2L stainless steel autoclave are pressed into the 0.5L hexane then in polymeric kettle, add certain density triethyl aluminum hexane solution.Open stirring then and add a certain amount of catalyzer, add the 1L hexane at last.Begin to heat up, and feed a certain amount of hydrogen and ethene, hydrogen alkene compares 0.28/0.45MPa.By the add-on of solenoid control ethene, make the stagnation pressure dimension of reaction system constant, by temperature controller controlled chilling discharge, make to be aggregated in 80 ℃ of following reactions two hours, close ethene then, stopped reaction.Cooling also bleeds off the still internal pressure, takes out polymerisate and suction filtration drying.The dry good product of weighing calculates catalyst activity, in PE.g/g.Ti; Measure bulk density and size-grade distribution simultaneously.Polymerization catalyst the results are shown in Table 1.
Embodiment 2
Prepare catalyst component with the method identical, but when the preparation catalyst component, ultrasonic frequency changes 40 ± 1KHZ into by 35 ± 1KHZ with embodiment 1.Ti (weight %) is 5.14%.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, but when the preparation catalyst component, ultrasonic frequency changes 30 ± 1KHZ into by 35 ± 1KHZ with embodiment 1.Ti (weight %) is 5.04%.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 with embodiment 1, but when the preparation catalyst component, ultrasonic frequency changes 50 ± 1KHZ into by 35 ± 1KHZ, ultrasonic time changed 30 minutes into by 60 minutes.Ti (weight %) is 4.99%.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 with embodiment 1, but when the preparation catalyst component, ultrasonic frequency changes 50 ± 1KHZ into by 35 ± 1KHZ, ultrasonic time changed 90 minutes into by 60 minutes.Only open the ultrasonic wave in front.Ti (weight %) is 4.89%.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 with embodiment 1, but when the preparation catalyst component, ultrasonic frequency changes 20 ± 1KHZ into by 35 ± 1KHZ, ultrasonic time changed 15 minutes into by 60 minutes.Only open a next ultrasonic wave.Ti (weight %) is 4.85%.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 use ultrasonic technology with embodiment 1.Ti (weight %) is 4.59%.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in table 1.
| Sample | Catalyst activity g.PE/g.cat | Polyethylene | |||||
| Bulk density g/ml | Size-grade distribution, wt% | ||||||
| ＞20 orders | 20-40 | 40-100 | 100-200 | ＜200 orders | |||
| Embodiment 1 | 687000 | 0.31 | 2 | 62 | 33 | 2 | 1 |
| Embodiment 2 | 651000 | 0.30 | 2 | 59 | 37 | 1 | 1 |
| Embodiment 3 | 683000 | 0.30 | 1 | 58 | 37 | 3 | 1 |
| Embodiment 4 | 652000 | 0.28 | 1 | 50 | 47 | 1 | 1 |
| Embodiment 5 | 593000 | 0.29 | 2 | 53 | 43 | 2 | 0 |
| Embodiment 6 | 584000 | 0.28 | 3 | 51 | 42 | 2 | 2 |
| Comparative example 1 | 484000 | 0.25 | 7 | 10 | 60 | 15 | 8 |
Annotate: polymerization appreciation condition: slurry polymerization, 80 ℃, 2.0hr, H
2/ C
==0.28MPa/0.45MPa
Claims (8)
1. the preparation method of a catalyst for ethylene polymerization, it is characterized in that: use ultrasonic technology in catalyst preparation process, this method may further comprise the steps:
A. under nitrogen protection inert solvent and quantitative organic ester being joined in the catalyzer synthesis reactor, stir under the room temperature, add magnesium chloride again, is that 0.01～0.5: 1 ratio adds in ester magnesium mol ratio, slowly is warming up to 50～70 ℃, keeps reaction 1～2 hour; Then slowly dripping one or more organic alcohol, is that 0.2～2.0: 1 ratio adds in the magnesium alkoxide mol ratio, keeps 50～70 ℃ of temperature in the kettle, constant temperature 1～2 hour; Open the ultrasonic wave 20～50KHZ that adjusts frequency, keep reaction 15～90 minutes, and keep 50～70 ℃ of temperature in the kettle;
B. stopping ultrasonic wave, was slowly to splash in the synthesis reactor at 0.05～1.0: 1 quantitative titanium tetrachloride by titanium magnesium mol ratio in 30～45 minutes, opened ultrasonic wave again, 20～50KHZ adjusts frequency, keep reaction 15-90 minute, stop ultrasonic wave, isothermal reaction 1～2 hour;
C. stop to stir, with upper strata mother liquor sucking-off, wash solid particulate with inert solvent, drying makes catalyzer.
2. according to the process of claim 1 wherein, the organic ester among the step a is selected from four titan-alkoxides;
Organic alcohol is preferably: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, isohexyl alcohol; Two process reaction temperature are preferably 60 ℃, preferred 1 hour of reaction times.
3. according to the process of claim 1 wherein, the organic ester among the step a is preferred: tetramethoxy titanium, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide.
4. according to the process of claim 1 wherein, the isothermal reaction time was excellent with 1 hour among the step b.
5. according to the process of claim 1 wherein the preferred 30～40KHZ of ultrasonic frequency among step a and the b, preferred 30～60 minutes of ultrasonic time; Ultrasonic wave is optional opens once or twice.
6. according to the process of claim 1 wherein, ultrasonic frequency 35 ± 1KHZ most preferably among step a and the b, preferred 60 minutes of ultrasonic time; Preferred two the opening of ultrasonic wave.
7. according to the process of claim 1 wherein, inert solvent is selected from C
5～C
15Alkane.
8. according to the process of claim 1 wherein, inert solvent is hexane more preferably.
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| 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 |
| CN102952222A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene resin and preparation method thereof |
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| CN103694384A (en) * | 2013-12-03 | 2014-04-02 | 临邑县鲁晶化工有限公司 | Preparation method of catalyst for ethylene polymerization or copolymerization |
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| CN1034579C (en) * | 1993-03-26 | 1997-04-16 | 化学工业部北京化工研究院 | Catalyst for ethylene polymerization or copolymerization |
| CN1216920C (en) * | 2002-12-11 | 2005-08-31 | 北京燕化高新技术股份有限公司 | Prepn process of polypropylene catalyst |
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| 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 |
| 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 |
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| 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 |
| CN109575164A (en) * | 2017-09-29 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method and applications of polyolefin catalyst |
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| CN109517097A (en) * | 2018-11-27 | 2019-03-26 | 山东鲁晶化工科技有限公司 | A kind of polyolefin catalyst, preparation method and application |
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