CN102863563B - Ultrahigh molecular polyethylene catalyst and preparation method - Google Patents
Ultrahigh molecular polyethylene catalyst and preparation method Download PDFInfo
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- CN102863563B CN102863563B CN201110185255.6A CN201110185255A CN102863563B CN 102863563 B CN102863563 B CN 102863563B CN 201110185255 A CN201110185255 A CN 201110185255A CN 102863563 B CN102863563 B CN 102863563B
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Abstract
The invention relates to a preparation method of an ultrahigh molecular polyethylene catalyst, which belongs to the high-molecular technical field. The method comprises the following steps: 1) under the protection of nitrogen, magnesium halide and a hydrocarbon solvent are reacted; 2) alcohol is added and forms an alcohol magnesium compound with magnesium halide; 3) halogenated alkyl aluminum and the alcohol magnesium compound form an intermediate product; 4) a supersonic wave device is switched on for performing ultrasonic treatment; 5) titanium tetrachloride is added and stirred for backflow under the heating condition; and 6) a standing process is carried out, the solid particles are washed and dried to obtain the ultrahigh molecular polyethylene catalyst. The obtained catalyst and cocatalyst alkyl aluminum are used together for synthesis of the ultrahigh molecular polyethylene. According to the invention, the ultrasonic treatment technology is used in the preparation process of the catalyst, the activity of the ultrahigh molecular polyethylene catalyst can be enhanced, the molecular weight of the polymerization products can be increased, the polymerization kinetics of the prepared catalyst is stable, and the polymerization technology can be easily controlled.
Description
Technical field
The present invention relates to a kind of extra high-molecular polythene catalyst and preparation method thereof, belong to technical field of macromolecules.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) refers to the linear structure polyethylene of viscosity-average molecular weight more than 1,500,000.Because UHMWPE molecular weight is even millions of up to 1,000,000, thereby there is the performances such as excellent shock-resistance, self lubricity, resistance to corrosive chemicals, stress cracking resistance, electrical insulating property, wear resistance.UHMWPE is widely used in the numerous areas such as weaving, papermaking (suction box cover), transport (liner in car, ship storehouse), packaging (bucket of dress sulfuric acid), machinery (guide rail, star wheel, mincer part), chemical industry (pump housing, valve body), mining, oil, agricultural, building, electrical equipment, medical treatment, physical culture and Refrigeration Technique because of its distinctive performance advantage, be particularly suitable for the parts of need of production higher building rationality energy, as transmitting gear, joint prosthesis part etc.; Can utilize in addition its high-strength modulus and high tensile to produce high strength fibre.In recent years, ultrahigh molecular weight polyethylene(UHMWPE) product is more and more subject to people's attention.
Now, the catalyzer of producing for UHMWPE mainly contains Ziegler-Natta(Z-N) type such as type, chromium system, metallocene.But up to the present, world wide class is still the most ripe, most widely used general with Z-N type UHMWPE catalyst technology.Z-N type UHMWPE catalyzer is a kind of carrier model effective catalyst.The key of preparing this catalyzer is the activation treatment of carrier magnesium halide.The activation of carrier magnesium halide mainly contains mechanical milling method and chemical reaction method.Chemical reaction method be by carrier magnesium halide and certain Lewis base as compound reacting forming complex solution such as alcohol, ester and ethers, add precipitation additive that carrier magnesium halide is separated out again, form the crystalline structure that is more conducive to active constituent loading.In the process of carrier activation, can use ultrasonic technology to change crystalline structure and the crystal grain size of carrier, thereby improve the titanium rate of carrying of catalyzer, and effectively improving the molecular weight of polymerisate, the polymerization catalyst reaction kinetics making is like this steady, is easy to polyreaction control.
UHMWPE granules of catalyst form heterogeneity prepared by traditional method, often has agglomeration to occur, and has suppressed to a great extent the abundant release of catalyst activity and has reduced the macro property of polymkeric substance.
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, last and titanium compound carries titanium reaction and makes required catalyzer, in reaction process, can add electron donor.
CN1861650A discloses a kind of preparation method of the Ziegler-Natta catalyst that can be used for ethylene thick liquid polymerizing, the method by being used hyperacoustic treatment technology in the preparation process of catalyzer, improve the titanium content of polyethylene catalysts, and effectively improve the size-grade distribution of polymkeric substance.
CN1506384A disclose a kind of by ultrasonic technology the preparation process for polypropylene catalyst, can improve the active and polymer stacks density of polypropylene catalyst.
Existing document is not found ultrasonic applications in the preparation process of extra high-molecular polythene catalyst, thereby is improved the activity of catalyzer and the report of polymericular weight.
Summary of the invention
The object of the present invention is to provide a kind of extra high-molecular polythene catalyst and preparation method thereof, catalyzer can make active ingredient effectively be carried on carrier, promotes the raising of catalyst activity and polymericular weight;
Preparation method is easy to control, and is convenient to implement.
Extra high-molecular polythene catalyst of the present invention, prepare in accordance with the following methods successively:
(1) magnesium halide and alcohol reaction form alcohol magnesium compound, and the add-on of alcohol, in the consumption of magnesium halide, is 0.1～6mol alcohol/1mol magnesium halide;
(2) alcohol magnesium compound and haloalkyl reactive aluminum form an intermediate product, and haloalkyl aluminium add-on, in the consumption of magnesium halide, is 0.5～3mol haloalkyl aluminium/1mol magnesium halide;
(3) utilize ultrasonic unit to process gained intermediate product, the ultrasonic unit power using is 30～200W, and frequency is 20～100KHz;
(4) add titanium compound reaction to obtain catalyzer, the add-on of titanium compound, in the consumption of magnesium halide, is 2～5mol titanium tetrachloride/1mol magnesium halide again.
In the present invention:
Described magnesium halide comprises: one or more in magnesium dihalide compound, alkoxyl group halogenated magnesium compound or alkyl halide magnesium compound, can be selected from magnesium chloride, methylmagnesium-chloride, methoxyl group chlorination magnesium, oxyethyl group magnesium chloride or butoxy magnesium chloride.
Described haloalkyl aluminium adopts general formula R
malCl
3-mrepresent, at least have a chlorine atom, wherein R is the alkyl with 1～10 carbon atom, and 1≤m < 3 can be selected from aluminium diethyl monochloride, dichloro one aluminium triethyl or chlorination dipropyl aluminium.
Described titanium compound general formula is Ti(OR
2)
ncl
4-n, wherein R
2be the alkyl that contains 1～6 carbon atom, n is 0～4, can be selected from titanium tetrachloride, tetrabutyl titanate or three butoxy titanium chlorides, preferably titanium tetrachloride.
The ultrasonic unit power using is preferably 40～150W, and frequency is 30～80KHz.
The method of extra high-molecular polythene catalyst of the present invention, comprises the following steps:
1) under nitrogen protection, a certain amount of magnesium halide is put into container, add hydrocarbon solvent, container is placed in to oil bath, open and stir, then add alcohol, heat up, at 40～130 DEG C, stir, reflux 0.5～3 hour;
2) slowly add haloalkyl aluminium and step 1) described in alcohol magnesium compound at 40～130 DEG C, stir, reflux 0.5～1 hour form intermediate product;
3) open ultrasonic unit, adjusting frequency is 20～100KHz, Modulating Power 30～200W, and the treatment time is 0.5～30 minute, still keeps reaction system to stir at 40～130 DEG C after closing ultrasonic unit, refluxes 0.5～2 hour;
4) slowly add titanium compound, at 40～130 DEG C, stir, reflux 1～3 hour;
5) stop stirring, leave standstill 1～30 minute, treat granules of catalyst sedimentation, layering, by supernatant liquid sucking-off, add hydrocarbon solvent washing solid particulate, so repetitive scrubbing, then make after drying catalyzer.
Wherein said hydrocarbon solvent comprises aliphatic compound or compound fragrant hydrocarbon, especially C
5～C
15aliphatic compound or compound fragrant hydrocarbon, as Skellysolve A, iso-pentane, hexane, heptane, octane, decane, benzene or toluene etc., preferably hexane or heptane.
Alcohol comprises the alcohol with 2～20 carbon atoms, preferably has the alcohol of 2～8 carbon atoms, as ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, isooctyl alcohol, 2-ethyl butanol or 2-Ethylhexyl Alcohol.
In the present invention:
Ultrasonication control: ultrasonic frequency is 20～100KHz, power 30～200W, the treatment time is 0.5～60 minute; After closing ultrasonic wave, still keep reaction system to stir at 40～130 DEG C, reflux 0.5～2 hour.
Preferably 40～150W of ultrasonic unit power, more preferably 40～80W;
Ultrasonic unit calibration 30～80KHz, more preferably 30～50KHz;
Ultrasonic treatment time preferably 0.5～30 minute, more preferably 1～10 minute.
Ultrasonic wave is a kind of elastic mechanical ripple in physical medium, and frequency is generally greater than 20 KHz, and it is a kind of physical energy form with electricity, magnetic, light etc. equally.Ultrasonic wave, because frequency is high, wavelength is short, has the characteristics such as pack, orientation and reflection, transmission.Ultrasonic wave has the effects such as mechanical effect, heat effect, cavitation effect to liquid medium.In the time there is ul-trasonic irradiation in liquid medium, ultrasonic wave density interphase ground makes liquid occur to flow to previous irradiation, causes that medium molecule vibrates centered by its equilibrium theory of tide.Ultrasonic wave makes to be present in the solid particulate fragmentation in liquid medium because of mechanical effect and emulsifying effect that concussion produces, and particle agglomeration phenomenon obviously reduces, and has improved the dispersiveness of solia particle in liquid medium.
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.
The catalyzer that adopts extra high-molecular polythene catalyst preparation method of the present invention to make, need to be used in conjunction with promotor, promotor adopts aluminum alkyls, the preferred trimethyl aluminium of aluminum alkyls, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dibutyl aluminum bromide and close compound, especially preferably triethyl aluminum.And it is 50～1500: 1 that the usage ratio between promotor can be controlled in Al/Ti mol ratio.
Ultrasonic unit of the present invention is that power frequency electricity is transformed into high frequency electrical signal more than 20KHz, be transported on transverter by high frequency cable, transverter can convert electric energy to strong ultrasonic vibration, when ultrasonic wave joins in catalyst preparation process, make the liquid phase substance in flask produce " cavitation effect ", in the time that ultrasonic wave is sparse, generate bubble, when extruding, crush bubble, produce around mechanical impulse force, this mechanical impulse action is to the carrier magnesium halide crystal that is scattered in normal hexane, can effectively impel the refinement of carrier granule size, homogeneous, subtract less granular agglomeration simultaneously, thereby change form and the size of carrier granule, active ingredient can be effectively carried on carrier, the final raising that promotes catalyst activity and polymericular weight, the polymerization catalyst reaction kinetics simultaneously making is steady, be 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 water in reaction vessels outside.
Using ultrasonic technology in the preparation process of UHMWPE catalyzer, can effectively impel refinement, the homogeneous of carrier granule size, subtract less granular agglomeration simultaneously, thereby change form and the size of carrier granule, active ingredient can be effectively carried on carrier, finally promote the raising of catalyst activity and polymericular weight.
The preparation method of extra high-molecular polythene catalyst of the present invention, compared with prior art has following beneficial effect:
(1) carrier magnesium halide is carried out short period of time ultrasonication and can effectively be improved activity and the resulting polymers molecular weight of extra high-molecular polythene catalyst.Adopt catalyzer of the present invention to carry out ethene slurry polymerization 1 hour at 0.6MPa, 60 DEG C, the polymerization activity of catalyzer can reach 50000gPE/gCat, and resulting polymers molecular weight can reach more than 5,000,000.
(2) catalyst reaction kinetics of the present invention is steady, and preparation method is easy to control, and is convenient to implement.
Brief description of the drawings
Fig. 1, kinetics of polymerization reaction graphic representation.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
In this specification sheets embodiment, the salient features testing method of catalyst performance and polymerisate is as follows:
The calculating of polymerization catalyst activity: the activity of catalyzer refers to the UHMWPE gross weight of polymerization gained in 1 hour and the ratio of catalyzer dosage.
Molecular weight determination: undertaken by ASTM-D4020-2005.Employing viscosimetry is measured, and makes solvent with perhydronaphthalene, and 135 DEG C of temperature, adopt Ubbelohde viscometer to measure the time that polyethylene solution flows out, and then calculate the intrinsic viscosity η of polymkeric substance.According to formula
M
γ=?5.37?×?10
4?×?[η]
1
.37
The M of gained
γbe 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, 1mol Magnesium Chloride Anhydrous, and add 5ml propyl carbinol, system temperature is increased to 70 DEG C, and at this temperature, keeps reaction to obtain alcohol magnesium compound solution after 0.5 hour; After being cooled to room temperature, slowly drip 30ml aluminium diethyl monochloride, at 70 DEG C, stir, reflux 0.5 hour; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains reaction 2 minutes.Close after ultrasonic unit, still keep reaction system isothermal reaction 0.5 hour at 70 DEG C; After being cooled to room temperature, slowly drip again 4ml titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C.Finally stop stirring, leave standstill, by supernatant liquid sucking-off, use hexane repetitive scrubbing three times, after being dried, obtain catalyzer.
Vinyl polymerization test
2L stainless steel polymeric kettle is no less than three times with high pure nitrogen displacement, then in polymeric kettle, add 1.2L normal hexane, add the certain density triethyl aluminum of 4ml and 1.5mg solid catalyst, open and stir rear rising system temperature to 60 DEG C, injecting ethene to system pressure is 0.6MPa, keeps temperature of reaction system, constant pressure, maintains polyreaction and lowers the temperature after 1 hour, discharging is also dry, can obtain extra high molecular polymer.Polymerization catalyst the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Embodiment 2
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 1 minute into by 2 minutes.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 3
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 5 minutes into by 2 minutes.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 4
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 8 minutes into by 2 minutes.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 5
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 30W into by 50W.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 6
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 80W into by 50W.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 7
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 150W into by 50W.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 8
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 20KHz into by 40KHz.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 9
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 30KHz into by 40KHz.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 10
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 60KHz into by 40KHz.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 11
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 80KHz into by 40KHz.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 12
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of propyl carbinol changes 4ml into by 5ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 13
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of propyl carbinol changes 6ml into by 5ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 14
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of aluminium diethyl monochloride changes 25ml into by 30ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 15
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of aluminium diethyl monochloride changes 20ml into by 30ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 16
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of titanium tetrachloride changes 3ml into by 4ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Embodiment 17
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, the dosage of titanium tetrachloride changes 5ml into by 4ml.Carry out polymerization with the identical method of embodiment 1 with this catalyst component.It the results are shown in Table 1.
Comparative example 1
By the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in Kaolinite Preparation of Catalyst process, do not use ultrasonic technology processing.When polyreaction, catalyzer dosage is that this catalyst component of 10mg carries out polymerization with the identical method of embodiment 1.It the results are shown in Table 1.
Table 1, embodiment result table
Claims (10)
1. an extra high-molecular polythene catalyst, it is characterized in that preparing in accordance with the following methods successively:
(1) magnesium halide and alcohol reaction form alcohol magnesium compound, and the add-on of alcohol, in the consumption of magnesium halide, is 0.1～6mol alcohol/1mol magnesium halide;
(2) alcohol magnesium compound and haloalkyl reactive aluminum form an intermediate product, and haloalkyl aluminium add-on, in the consumption of magnesium halide, is 0.5～3mol haloalkyl aluminium/1mol magnesium halide;
(3) utilize ultrasonic unit to process gained intermediate product, the ultrasonic unit power using is 30～200W, and frequency is 20～100KHz;
(4) add titanium compound reaction to obtain catalyzer, the add-on of titanium compound, in the consumption of magnesium halide, is 2～5mol titanium compound/1mol magnesium halide again;
Meanwhile, also further comprise promotor aluminum alkyls, described aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride or dibutyl aluminum bromide; And it is 50～1500: 1 that the usage ratio between promotor is controlled at Al/Ti mol ratio.
2. extra high-molecular polythene catalyst according to claim 1, is characterized in that described magnesium halide comprises: one or more in magnesium dihalide compound, alkoxyl group halogenated magnesium compound or alkyl halide magnesium compound.
3. extra high-molecular polythene catalyst according to claim 2, is characterized in that described magnesium halide is selected from magnesium chloride, methylmagnesium-chloride, methoxyl group chlorination magnesium, oxyethyl group magnesium chloride or butoxy magnesium chloride.
4. extra high-molecular polythene catalyst according to claim 1, is characterized in that described haloalkyl aluminium adopts general formula R
malCl
3-mrepresent, wherein R is the alkyl with 1～10 carbon atom, 1≤m < 3.
5. extra high-molecular polythene catalyst according to claim 4, is characterized in that described haloalkyl aluminium is selected from aluminium diethyl monochloride, dichloro one aluminium triethyl or chlorination dipropyl aluminium.
6. extra high-molecular polythene catalyst according to claim 1, is characterized in that described titanium compound general formula is Ti(OR
2)
ncl
4-n, wherein R
2be the alkyl that contains 1～6 carbon atom, n is 0～4.
7. extra high-molecular polythene catalyst according to claim 6, is characterized in that described titanium compound is titanium tetrachloride, tetrabutyl titanate or three butoxy titanium chlorides.
8. extra high-molecular polythene catalyst according to claim 1, is characterized in that used ultrasonic unit power is 40～150W, and frequency is 30～80KHz.
9. prepare a method for the described extra high-molecular polythene catalyst of one of claim 1-8, it is characterized in that catalyzer and the promotor prepared by following method are used in conjunction with;
Comprise the following steps:
1) under nitrogen protection, a certain amount of magnesium halide is put into container, add hydrocarbon solvent, container is placed in to oil bath, open and stir, then add alcohol, heat up, at 40～130 DEG C, stir, reflux 0.5～3 hour;
2) slowly add haloalkyl aluminium and step 1) described in alcohol magnesium compound at 40～130 DEG C, stir, reflux 0.5～1 hour form intermediate product;
3) open ultrasonic unit, adjusting frequency is 20～100KHz, Modulating Power 30～200W, and the treatment time is 0.5～30 minute, still keeps reaction system to stir at 40～130 DEG C after closing ultrasonic unit, refluxes 0.5～2 hour;
4) slowly add titanium compound, at 40～130 DEG C, stir, reflux 1～3 hour;
5) stop stirring, leave standstill 1～30 minute, treat granules of catalyst sedimentation, layering, by supernatant liquid sucking-off, add hydrocarbon solvent washing solid particulate, so repetitive scrubbing, then make after drying catalyzer.
10. preparation method according to claim 9, is characterized in that described hydrocarbon solvent is Skellysolve A, iso-pentane, hexane, heptane, octane, decane, benzene or toluene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110185255.6A CN102863563B (en) | 2011-07-04 | 2011-07-04 | Ultrahigh molecular polyethylene catalyst and preparation method |
| SG2012049359A SG186588A1 (en) | 2011-07-04 | 2012-07-03 | An ultra high molecular weight polyethylene catalyst and a process for the preparation thereof |
| US13/540,982 US20130012375A1 (en) | 2011-07-04 | 2012-07-03 | Ultra high molecular weight polyethylene catalysts and processes 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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| CN201110185255.6A CN102863563B (en) | 2011-07-04 | 2011-07-04 | Ultrahigh molecular polyethylene catalyst 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 |
| CN104558294B (en) * | 2013-10-15 | 2017-01-18 | 中国石油化工股份有限公司 | Ultrahigh-molecular weight polyethylene catalyst and preparation method thereof |
| CN103694384B (en) * | 2013-12-03 | 2016-09-28 | 临邑县鲁晶化工有限公司 | A kind of for vinyl polymerization or the preparation method of copolymerization catalyst |
| EP2907829B1 (en) * | 2014-02-13 | 2020-08-19 | Borealis AG | Disentangled high or ultrahigh molecular weight polyethylene prepared with Ziegler-Natta catalyst |
| CN113185627B (en) * | 2021-05-20 | 2023-04-14 | 任丘市利和科技发展有限公司 | Catalyst component for ultra-high molecular weight polyethylene, preparation method and application thereof |
| CN116333193B (en) * | 2023-05-22 | 2024-02-02 | 上海优铖工逸技术有限公司 | Ziegler Natta catalyst, preparation method and application thereof |
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 CN201110185255.6A patent/CN102863563B/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 |
Non-Patent Citations (1)
| Title |
|---|
| JP昭60-192711A 1985.10.01 * |
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