CN102863564B - High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method - Google Patents
High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method Download PDFInfo
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- CN102863564B CN102863564B CN201110185502.2A CN201110185502A CN102863564B CN 102863564 B CN102863564 B CN 102863564B CN 201110185502 A CN201110185502 A CN 201110185502A CN 102863564 B CN102863564 B CN 102863564B
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Abstract
The invention discloses a high activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and a preparation method, the catalyst is prepared by reacting a magnesium halide carrier, a titanium compound, at least one organic alcohol and at least one halogen substituted aluminum alkyl compound; the method comprises the following steps: 1) under certain temperature, magnesium halide and alcohol are reacted; 2) after completely dissolving, the product obtained in the step 1) is reacted with chlorinated alkyl aluminum and a titanium compound in order; 3) a supersonic wave apparatus is used for treating the product in the step 2); and 4) removing a solvent in the product obtained in the step 3) to obtain the high activity catalyst. The high activity catalyst and a cocatalyst should be used together for polymerization, and can be used for synthesizing ultrahigh molecular weight polyethylene resin. According to the invention, an ultrasonic treatment technology is used, so that final catalyst particle form is controlled, the polymerization efficiency of the catalyst can be effectively improved, the stabilization of polymerization dynamics can be guaranteed, and the molecular weight of the polymerization product is high.
Description
Technical field
The present invention relates to a kind ofly for synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) and preparation method thereof, especially adopt ultrasonication for the synthesis of ultrahigh molecular weight polyethylene(UHMWPE) high activated catalyst and preparation method thereof.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (being called for short UHMWPE) typically refers to viscosity-average molecular weight 1.5 × 10
6above linear structure polyethylene, because UHMWPE molecular weight is even millions of up to 1,000,000, thereby has excellent stress cracking resistance, electrical insulating property, wear resistance etc.Be particularly suitable for the parts of need of production higher building rationality energy, as transmitting gear, joint prosthesis part etc.UHMWPE is compared with common high molecular polyolefine, and the excellences such as acoustic resistance, radiation resistance, thermotolerance, moistureproofness, tensile property, have caused the power of people's synthesizing super high molecular weight polyethylene thus.And research shows: in UHMWPE synthetic, resin exists the phenomenon of so-called " copying " with catalyzer, thereby, can play by controlling the form of catalyzer the effect of effectively controlling resin form and improving polymerization efficiency.
Up to the present, the synthetic of UHMWPE is still most widely used with Ziegler-Natta type catalyzer.Ziegler-Natta type catalyzer, since coming out, has experienced by the first-generation to the development in four generations, and catalytic performance improves constantly, and has promoted the fast development of polyolefin industry.At present the research-and-development activity of this class catalyzer is mainly concentrated on to the development of high activated catalyst and in the control of polyolefine apparent density and microtexture.
Mitsui company discloses a kind of preparation method of the catalyzer for vinyl polymerization and copolymerization in JP49-51378: the magnesium dichloride at mineral oil medium through grinding and ethanol synthesis generate alcohol adduct slurries, remove most of ethanol with aluminium diethyl monochloride generation esterification again, finally use TiCl
4carry Ti reaction, obtain Ti/MgCl
2carried catalyst is the PZ catalyzer of industrial widespread use.But in the preparation process of catalyzer, the irregular platy shaped particle producing when carrier magnesium chloride exists former grinding in slurry reaction system, causes the solid catalyst particle form that obtains poor, and thickness is inhomogeneous, thereby polymer morphology is poor, and fine powder is many.
A series of Ziegler-Natta type catalyzer are disclosed in CN1099041A, CN1229092, CN85100997, the shortcoming of this traditional method is that granules of catalyst is to control by precipitation process completely, its particle diameter and size distribution are difficult to control, because difficulty is reclaimed in the use that has a large amount of liquid titanium compounds, polymerization activity is also difficult to control.Meanwhile, the size distribution of the polymkeric substance of gained is wider, and particle diameter is also difficult to control.
CN101074275A discloses a kind of preparation method of extra high-molecular polythene catalyst, the method is mainly to react with alkylol cpd, titanate ester compound by halogenated magnesium compound to form alcohol magnesium compound, use again the dealcoholysis of chlorination aluminum alkyls, finally titanium compound is loaded to carrier and makes required catalyzer, in reaction process, need to add electron donor.The UHMWPE catalyzer that the method makes has high reactivity and polymerisate and has the feature of high bulk density, and activity can reach 20000g PE (gCat)
-1h
-1.
Ultrasonic wave refers to the elastic wave that frequency produces in medium higher than the object of 20kHz.The applicable field of ultrasonic wave is very extensive, and in chemical industry, hyperacoustic application also more and more comes into one's own, and has produced thus an emerging cross discipline--sonochemistry.Hyperacoustic chemokinesis, is mainly derived from its cavitation phenomenon.So-called ultrasonic cavitation refers to that the micro-bubble being present in liquid phase vibrates, grows, collapses closed process under the effect of ultrasonic field, is acoustochemical energy derive.Become the focus of research in catalytic field sonochemistry, especially, in catalyst preparation process, by ultrasonication, can increase the specific surface area of catalyzer, made active ingredient disperse better thereby improve the activity of catalyzer.
CN1861650A discloses a kind of preparation method of the Ziegler-Natta catalyst that can be used for ethylene thick liquid polymerizing, the method by carrier activate, load two steps in active centre carry out ultrasonication, improve the Ti content of this catalyzer, and effectively improved the size-grade distribution of polymkeric substance.
CN1506384A disclose a kind of by ultrasonic technology the preparation method for polypropylene catalyst, the method is by being used hyperacoustic treatment technology in support of the catalyst reactivation process, improved the active and polymer stacks density of polypropylene catalyst.
With difference of the present invention, CN1861650A and CN1506384A are the organosilane esters having added in carrier reactivation process containing Ti, and do not adopt haloalkyl aluminum compound as precipitation agent; Ultrasonication is only as carrier activation step, and to control carrier form, final catalyzer forms and still relies on precipitation process.CN1861650A rises to 42% for ethylene polymerization activity under square one, and the present invention improves more than 90% under square one.
And also do not find in the loading process of active centre in the patent of preparing at existing UHMPWE catalyzer, pass through ul-trasonic irradiation, make catalyst grain size even, improve catalyst reaction specific surface area, finally improve the report of molecular resin amount and UHMWPE polymerization catalyst efficiency simultaneously.
Summary of the invention
The object of the present invention is to provide and a kind ofly in preparation process, utilize that ultrasonication synthesized polymer efficiency is high, reaction kinetics steadily, polyethylene catalysts that the polymericular weight that generates is high and preparation method thereof.
The present invention is for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE), and by magnesium halide carrier, titanium compound, at least one Organic Alcohol is made with the alkylaluminium cpd reaction that has at least a halogen to replace, wherein:
(1) magnesium halide is magnesium chloride, methylmagnesium-chloride, the mixture of one or more in methoxyl group chlorination magnesium, oxyethyl group magnesium chloride or butoxy magnesium chloride;
(2) titanium compound is one or more the mixture in titanium tetrachloride, titanous chloride or tetrabutyl titanate, and consumption is 2～10molTi/1molMg;
(3) Organic Alcohol is C
2～C
20the alcohol of straight chain, side chain or cycloalkyl, consumption is 1～20molXOH/1molMg;
(4) general formula of the alkylaluminium cpd that halogen replaces is R
nalX
3-n, in formula, R is C
1～C
10alkyl, X is halogen, n is integer, 1≤n < 3, consumption is 0.5～6molAl/1molMg.
Described magnesium halide is magnesium chloride.
Described titanium compound is titanium tetrachloride.
Described Organic Alcohol is C
2～C
8alcohol, preferred alcohol, n-propyl alcohol, propyl carbinol, isopropylcarbinol or isooctyl alcohol, further preferably propyl carbinol.The propyl carbinol that the preferred polarity of the present invention is lower, and in active constituent loading process, adopt ultrasonic technology control granules of catalyst form, increase the specific surface area of catalyzer, improve polymerization catalyst activity.
The alkylaluminium cpd that described halogen replaces is aluminium diethyl monochloride, dichloro one aluminium triethyl or chlorination dipropyl aluminium, preferably aluminium diethyl monochloride.
The described preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE), comprises the steps:
(1) under nitrogen protection, magnesium halide is put into there-necked flask, add a certain amount of inert solvent, the oil bath that there-necked flask is placed in to design temperature, opens and stirs;
(2) add Organic Alcohol, stir 0.1～1 hour at 50～100 DEG C, react, treat solution clear, now, added alcohol and magnesium halide form a kind of alcohol magnesium compound, and the consumption of Organic Alcohol is 1～20molXOH/1molMg;
(3) in alcohol magnesium compound, slowly drip the alkylaluminium cpd that halogen replaces, at 50～100 DEG C, stir, reflux 0.5～2 hour, obtain the aaerosol solution of magnesium halide, the consumption of the alkylaluminium cpd that halogen replaces is 0.5～6molAl/1molMg;
(4) slowly drip titanium compound at the aaerosol solution of magnesium halide, at 50～100 DEG C, stir, reflux 2～4 hours, the consumption of titanium compound is 2～10molTi/1molMg;
(5) solution step (4) being made carries out supersound process: frequency 20～80KHz, and power 30～150W, the treatment time is 0.5～30 minute;
(6) stop stirring, leave standstill 3～10 minutes, treat granules of catalyst sedimentation, layering, by supernatant liquid sucking-off, add hydrocarbon solvent washing solid particulate, so repetitive scrubbing 3 times; After dry at 70～120 DEG C, make.
Described inert solvent is selected C
5～C
15alkane, preferably C
5～C
10alkane, further preferably hexane.
Preferably 40～the 60W of ultrasonic unit power using.
The ultrasonic treatment time using preferably 1～15 minute, further preferably 3～6 minutes.
High activated catalyst of the present invention need be with promotor together for polyreaction, can be for the synthesis of polyvinyl resin with super-high molecular weight, and described promotor is alkylaluminium cpd:
Trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride or methylaluminoxane, preferably triethyl aluminum.
The present invention in the loading process of extra high-molecular polythene catalyst active centre by catalyzer being carried out to the ultrasonication of certain hour, can obtain highly active extra high-molecular polythene catalyst, and the molecular weight of gained ultrahigh molecular weight polyethylene(UHMWPE) has obtained effective raising, this polymerization catalyst reaction kinetics is steady simultaneously, is easy to polymerization technique control.
The present invention adopts ultrasonic technology that catalyst activity is had a more substantial increase in the loading process of active centre, and catalytic efficiency reaches 70000gPE (gCat)
-1h
-1.Ultrasonic treatment time is too short by limited to the action effect of carrier magnesium halide crystal, be difficult to effectively improve the activity of catalyzer, but ultrasonic treatment time is long by the crystal habit of havoc carrier magnesium halide, and this will directly affect morphology.
Ultrasonic unit of the present invention is that power frequency electricity is transformed into high frequency electrical signal more than 20KHz, is transported on transverter by high frequency cable, and transverter can convert electric energy to strong ultrasonic vibration.In catalyst preparation process, the high energy " cavitation effect " that utilizes ultrasonic wave to produce, can effectively reduce the median size of catalyzer, it is even that size-grade distribution is tending towards more, the reaction specific surface area of the catalyzer that further raising finally makes, the final raising that promotes catalyst activity and polymericular weight, the polymerization catalyst reaction kinetics simultaneously making is steady, is easy to polyreaction control.
Ultrasonic unit of the present invention can be to insert in glass reaction vessel and directly act on reaction system with probe form, also can act on reaction system by liquid phase in reaction vessels outside.
Beneficial effect of the present invention is as follows:
(1) the present invention, in catalyst preparation process, can effectively improve the molecular weight of polymerization efficiency and gained resin by ultrasonication.Adopt high activated catalyst of the present invention to be used in conjunction with promotor triethyl aluminum, under 0.6MPa, 60 DEG C of polymerizing conditions, carry out ethene slurry polymerization 1 hour, the polymerization activity of catalyzer can reach 70000gPE (gCat)
-1, resulting polymers molecular weight can reach 400 × 10
4above.
(2) catalyzer of the present invention has high reactivity and reaction kinetics feature stably, is easier to the control of polyreaction in polymerization process, and in the polymerization process of 1 hour, catalyst activity has no obvious decay.
Brief description of the drawings
Fig. 1 is kinetics of polymerization reaction graphic representation.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
In the embodiment of the present invention, the test of the salient features of catalyst performance and polymerisate adopts following methods to carry out:
Polymerization efficiency: the ratio of certain hour inner catalyst polymerization gained resin quality and Primary Catalysts quality, that is:
Molecular weight determination: undertaken by ASTM-D4020-2005.Make solvent with perhydronaphthalene, 135 DEG C of temperature, adopt Ubbelohde viscometer to measure the polyethylene solution elution time, then calculate the intrinsic viscosity η of polymkeric substance.Calculation formula is as follows:
M
γ＝5.37×10
4×[η]
1.37
M in formula
γfor the molecular weight of polymkeric substance.
Embodiment 1
Catalyzer preparation:
First, by with heating system and be furnished with whipping appts and the there-necked flask of the 250ml of reflux condensation mode system nitrogen replacement is no less than three times, then add 60ml normal hexane, 1g Magnesium Chloride Anhydrous, stirs heat up (65 DEG C of Temperature Settings); Add subsequently propyl carbinol 5ml, stir and obtain alcohol magnesium compound solution after 0.3 hour; After being cooled to room temperature, slowly drip 2.8 × 10
-4mol aluminium diethyl monochloride refluxes 1 hour at 65 DEG C; After being cooled to room temperature, slowly drip 4 × 10 again
-4mol titanium tetrachloride, isothermal reaction 0.5 hour at 70 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 1min.Close after ultrasonic unit, still keep reaction system isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, use hexane repetitive scrubbing three times, after being dried, obtain catalyzer.
Vinyl polymerization test
2L stainless steel polymeric kettle is vacuumized with high pure nitrogen and replaces and be no less than three times, then in polymeric kettle, add 1.2L normal hexane, add 2.4 × 10
-3mol triethyl aluminum and 1.5mg solid catalyst, open and stir rear rising system temperature to 60 DEG C, and being filled with ethene to polymeric kettle pressure is 0.6MPa, holding temperature, constant pressure carry out polyreaction, lower the temperature after 1 hour until polyreaction, discharging is also dry, obtains polyvinyl resin with super-high molecular weight.The molecular weight of polymerization catalyst efficiency and resin is in table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Embodiment 2
The preparation method of catalyst component is with embodiment 1, but in Kaolinite Preparation of Catalyst process, changes the time of hyperacoustic processing into 2min by 1min.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 3
The preparation method of catalyst component is with embodiment 1, but in Kaolinite Preparation of Catalyst process, changes the time of hyperacoustic processing into 5min by 1min.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Embodiment 4
The preparation method of catalyst component is with embodiment 1, but in Kaolinite Preparation of Catalyst process, changes the time of hyperacoustic processing into 20min by 1min.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 5
Catalyst component preparation method is with embodiment 2, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 30W into by 50W.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 6
Catalyst component preparation method is with embodiment 2, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 80W into by 50W.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 7
Catalyst component preparation method is with embodiment 2, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 150W into by 50W.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 8
Propyl carbinol in embodiment 2 changes ethanol into, and dosage is 3ml, and other catalyst components preparation method is with embodiment 2.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 9
Titanium tetrachloride in embodiment 2 changes tetrabutyl titanate into, and dosage is same, and other catalyst components preparation method is with embodiment 2.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 10
Titanium tetrachloride in embodiment 2 changes titanous chloride into, and dosage is same, and other catalyst components preparation method is with embodiment 2.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Embodiment 11
Propyl carbinol in embodiment 2 changes Virahol into, and dosage is same, and other catalyst components preparation method is with embodiment 2.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1.
Comparative example 1
The preparation method of catalyst component is with embodiment 1, but in Kaolinite Preparation of Catalyst process, do not use ultrasonic technology processing.Vinyl polymerization is tested with embodiment 1, and it the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Table 1 resin detects analytical table
Claims (9)
1. for a preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE), it is characterized in that comprising the steps:
(1) under nitrogen protection, magnesium halide stirs 0.1～1 hour with Organic Alcohol after being dissolved in inert solvent at 50～100 DEG C, reacts, and generates alcohol magnesium compound in the time of solution clear, and the consumption of Organic Alcohol is 1～20molXOH/1molMg;
(2) alkylaluminium cpd that adds halogen to replace in alcohol magnesium compound stirs at 50～100 DEG C, refluxes 0.5～2 hour, obtains the aaerosol solution of magnesium halide, and the consumption of the alkylaluminium cpd that halogen replaces is 0.5～6molAl/1molMg;
(3) add titanium compound at the aaerosol solution of magnesium halide, at 50～100 DEG C, stir, reflux 2～4 hours, the consumption of titanium compound is 2～10molTi/1molMg;
(4) solution step (3) being made carries out supersound process: frequency 20～80KHz, and power 30～150W, the treatment time is 0.5～30 minute;
(5) solution after supersound process is carried out particles settling, layering, washing, makes powder catalyst after dry;
This catalyzer, by magnesium halide carrier, titanium compound, at least one Organic Alcohol with have at least the alkylaluminium cpd reaction that halogen replaces to make, wherein:
Magnesium halide is magnesium chloride, methylmagnesium-chloride, the mixture of one or more in methoxyl group chlorination magnesium, oxyethyl group magnesium chloride or butoxy magnesium chloride;
Titanium compound is one or more the mixture in titanium tetrachloride, titanous chloride or tetrabutyl titanate, and consumption is 2～10molTi/1molMg;
Organic Alcohol is C
2～C
20the alcohol of straight chain, side chain or cycloalkyl, consumption is 1～20molXOH/1molMg;
The general formula of the alkylaluminium cpd that halogen replaces is R
nalX
3-n, in formula, R is C
1～C
10alkyl, X is halogen, n is integer, 1≤n < 3, consumption is 0.5～6molAl/1molMg.
2. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that described magnesium halide is magnesium chloride.
3. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that described titanium compound is titanium tetrachloride.
4. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that described Organic Alcohol is C
2～C
8alcohol.
5. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 4, is characterized in that described Organic Alcohol is propyl carbinol.
6. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that the alkylaluminium cpd that described halogen replaces is aluminium diethyl monochloride, dichloro one aluminium triethyl or chlorination dipropyl aluminium.
7. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that the described inert solvent of step (1) is C
5~ C
15alkane.
8. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that the described supersound process power of step (4) is 40～60W.
9. the preparation method for the synthetic high activated catalyst of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1, is characterized in that the described supersound process time of step (4) is 3～6 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110185502.2A CN102863564B (en) | 2011-07-04 | 2011-07-04 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
| US13/540,982 US20130012375A1 (en) | 2011-07-04 | 2012-07-03 | Ultra high molecular weight polyethylene catalysts and processes for the preparation thereof |
| SG2012049359A SG186588A1 (en) | 2011-07-04 | 2012-07-03 | An ultra high molecular weight polyethylene catalyst and a process for the preparation thereof |
| MYPI2012003055A MY173483A (en) | 2011-07-04 | 2012-07-04 | An ultra high molecular weight polyethylene catalyst and a process for the preparation thereof |
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| CN201110185502.2A CN102863564B (en) | 2011-07-04 | 2011-07-04 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
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| CN103772560B (en) * | 2012-10-22 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of fiber polyvinyl resin with super-high molecular weight and preparation method 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
| CN1506384A (en) * | 2002-12-11 | 2004-06-23 | 北京燕化高新技术股份有限公司 | Prepn process of polypropylene catalyst |
| CN1861650A (en) * | 2005-05-12 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| CN101074275A (en) * | 2007-06-22 | 2007-11-21 | 上海化工研究院 | Extra high-molecular polythene catalyst and its production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0629287B2 (en) * | 1984-03-14 | 1994-04-20 | 三菱油化株式会社 | Olefin polymerization catalyst component |
-
2011
- 2011-07-04 CN CN201110185502.2A patent/CN102863564B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
| CN1506384A (en) * | 2002-12-11 | 2004-06-23 | 北京燕化高新技术股份有限公司 | Prepn process of polypropylene catalyst |
| CN1861650A (en) * | 2005-05-12 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| CN101074275A (en) * | 2007-06-22 | 2007-11-21 | 上海化工研究院 | Extra high-molecular polythene catalyst and its production |
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| Title |
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| JP昭60-192711A 1985.10.01 * |
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