CN102863563A - Ultrahigh molecular polyethylene catalyst and preparation method - Google Patents
Ultrahigh molecular polyethylene catalyst and preparation method Download PDFInfo
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- CN102863563A CN102863563A CN2011101852556A CN201110185255A CN102863563A CN 102863563 A CN102863563 A CN 102863563A CN 2011101852556 A CN2011101852556 A CN 2011101852556A CN 201110185255 A CN201110185255 A CN 201110185255A CN 102863563 A CN102863563 A CN 102863563A
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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 that viscosity-average molecular weight is at the linear structure polyethylene more than 1,500,000.Because the UHMWPE molecular weight is up to 1,000,000 even millions of, thereby have 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), transportation (liner in car, ship storehouse), packing (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 the rational energy of need of production higher building, such as transmitting gear, joint prosthesis spare etc.; Can utilize in addition its high-strength modulus and high tensile to produce high strength fibre.In recent years, the ultrahigh molecular weight polyethylene(UHMWPE) product more and more is subject to people's attention.
Now, be used for the catalyzer that UHMWPE produces and mainly contain Ziegler-Natta(Z-N) types such as type, chromium system, metallocene.But up to the present, the 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 for 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 with carrier magnesium halide and certain Lewis base such as compound reacting forming complex solution such as alcohol, ester and ethers, add precipitation additive so that the 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 the molecular weight of Effective Raise polymerisate, the polymerization catalyst reaction kinetics that makes like this is steady, is easy to polyreaction control.
The UHMWPE granules of catalyst form heterogeneity of traditional method preparation 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 mainly is to form pure magnesium compound by halogenated magnesium compound and alkylol cpd, the reaction of titanate ester compound, use again the dealcoholysis of chlorination aluminum alkyls, last and titanium compound carries the titanium reaction and makes required catalyzer, can add electron donor in the reaction process.
CN1861650A discloses a kind of preparation method who can be used for the Ziegler-Natta catalyst of ethylene thick liquid polymerizing, the method is by using 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 discloses a kind of preparation process that ultrasonic technology is used for polypropylene catalyst, can improve polypropylene catalyst activity and polymer stacks density.
Existing document is not found the preparation process of ultrasonic applications in 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 the carrier, promotes the raising of catalyst activity and polymericular weight;
The preparation method is easy to control, is convenient to implement.
Extra high-molecular polythene catalyst of the present invention prepares successively in accordance with the following methods:
(1) magnesium halide and alcohol reaction form pure magnesium compound, and the add-on of alcohol is 0.1～6mol alcohol/1mol magnesium halide in the consumption of magnesium halide;
(2) pure magnesium compound and haloalkyl reactive aluminum form an intermediate product, and haloalkyl aluminium add-on is 0.5～3mol haloalkyl aluminium/1mol magnesium halide in the consumption of magnesium halide;
(3) utilize ultrasonic unit that the gained intermediate product is processed, employed ultrasonic unit power is 30～200W, and frequency is 20～100KHz;
(4) add the titanium compound reaction again and obtain catalyzer, the add-on of titanium compound is 2～5mol titanium tetrachloride/1mol magnesium halide in the consumption of magnesium halide.
Among the present invention:
Described magnesium halide comprises: one or more in magnesium dihalide compound, alkoxyl group halogenated magnesium compound or the 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-mExpression has a chlorine atom at least, and 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, R wherein
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, preferred titanium tetrachloride.
Employed ultrasonic unit power is preferably 40～150W, and frequency is 30～80KHz.
The method of extra high-molecular polythene catalyst of the present invention may further comprise the steps:
1) under the nitrogen protection, a certain amount of magnesium halide is put into container, add hydrocarbon solvent, container is placed oil bath, open and stir, add again alcohol, heat up, in 40～130 ℃ of lower stirrings, refluxed 0.5～3 hour;
2) slowly add haloalkyl aluminium and step 1) described in pure magnesium compound in 40～130 ℃ of lower stirrings, 0.5～1 hour formation intermediate product refluxes;
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 40～130 ℃ of lower stirrings after closing ultrasonic unit, refluxes 0.5～2 hour;
4) slowly add titanium compound, in 40～130 ℃ of lower stirrings, refluxed 1～3 hour;
5) stop to stir, left standstill 1～30 minute, treat granules of catalyst sedimentation, layering, with the supernatant liquid sucking-off, add hydrocarbon solvent washing solid particulate, so repetitive scrubbing makes catalyzer more after drying.
Wherein said hydrocarbon solvent comprises aliphatic compound or compound fragrant hydrocarbon, especially C
5～C
15Aliphatic compound or compound fragrant hydrocarbon, such as Skellysolve A, iso-pentane, hexane, heptane, octane, decane, benzene or toluene etc., preferred hexane or heptane.
Alcohol comprises the alcohol with 2～20 carbon atoms, preferably has the alcohol of 2～8 carbon atoms, such as ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, isooctyl alcohol, 2-ethyl butanol or 2-Ethylhexyl Alcohol.
Among the present invention:
Ultrasonication control: ultrasonic frequency is 20～100KHz, power 30～200W, and the treatment time is 0.5～60 minute; Still keep reaction system 40～130 ℃ of lower stirrings after closing ultrasonic wave, refluxed 0.5～2 hour.
Preferred 40～the 150W of ultrasonic unit power, more preferably 40～80W;
Preferred 0.5～30 minute of ultrasonic treatment time, more preferably 1～10 minute.
Ultrasonic wave is a kind of elastic mechanical ripple in the 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 is 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.When having ul-trasonic irradiation in the liquid medium, ultrasonic wave density interphase ground makes liquid occur to flow to previous irradiation, causes medium molecule vibration-generating centered by its equilibrium theory of tide.Ultrasonic wave makes the solid particulate that is present in the liquid medium broken because of mechanical effect and the emulsifying effect that concussion produces, and the particle agglomeration phenomenon obviously reduces, and has improved the dispersiveness of solia particle in liquid medium.
Ultrasonic treatment time is too short will be limited to the action effect of carrier magnesium halide crystal, be difficult to the activity of Effective Raise catalyzer, but the long crystal habit with havoc carrier magnesium halide of ultrasonic treatment time, 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 preferred triethyl aluminum.And it is 50～1500: 1 that the usage ratio between the promotor can be controlled in the Al/Ti mol ratio.
Ultrasonic unit of the present invention is that the power frequency electricity is transformed into high frequency electrical signal more than the 20KHz, be transported on the transverter by high frequency cable, transverter can convert electric energy to strong ultrasonic vibration, when ultrasonic wave joins in the catalyst preparation process, so that the liquid phase substance in the flask produces " cavitation effect ", when ultrasonic wave is sparse, generate bubble, crushing bubble during extruding, 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 simultaneously less granular agglomeration, thereby change form and the size of carrier granule, active ingredient can effectively be carried on the carrier, the final raising that promotes catalyst activity and polymericular weight, the polymerization catalyst reaction kinetics that makes simultaneously is steady, is easy to polyreaction control.
Ultrasonic unit of the present invention can be to insert in the glass reaction vessel with the probe form to directly act on reaction system, also can act on reaction system by water in the reaction vessels outside.
Using ultrasonic technology in the preparation process of UHMWPE catalyzer, can effectively impel refinement, the homogeneous of carrier granule size, subtract simultaneously less granular agglomeration, thereby change form and the size of carrier granule, active ingredient can effectively be carried on the 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) the carrier magnesium halide is carried out activity and the resulting polymers molecular weight that the short period of time ultrasonication gets final product the Effective Raise extra high-molecular polythene catalyst.Adopt catalyzer of the present invention to carry out the ethene slurry polymerization 1 hour under 0.6MPa, 60 ℃, the polymerization activity of catalyzer can reach 50000gPE/gCat, and the resulting polymers molecular weight can reach more than 5,000,000.
(2) catalyst reaction kinetics of the present invention is steady, and the preparation method is easy to control, is convenient to implement.
Description of drawings
Fig. 1, kinetics of polymerization reaction graphic representation.
Embodiment
The invention will be further described below in conjunction with embodiment.
The salient features testing method of catalyst performance and polymerisate is as follows among this specification sheets embodiment:
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.The employing viscosimetry is measured, and makes solvent with perhydronaphthalene, and 135 ℃ 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
The catalyzer preparation
To and be furnished with whipping appts and the there-necked flask of the 250ml of reflux condensation mode system is no less than three times with nitrogen replacement with heating system first, then add the 60ml normal hexane, the 1mol Magnesium Chloride Anhydrous, and adding 5ml propyl carbinol, system temperature is increased to 70 ℃, and is keeping reaction to obtain pure magnesium compound solution after 0.5 hour under this temperature; Slowly drip the 30ml aluminium diethyl monochloride after being cooled to room temperature, 70 ℃ of lower stirrings, backflow 0.5 hour; Open ultrasonic unit, adjusting frequency is 40KHz, and rating of set is 50W, keeps reaction 2 minutes.After closing ultrasonic unit, still keep reaction system 70 ℃ of lower isothermal reactions 0.5 hour; Slowly drip again the 4ml titanium tetrachloride after being cooled to room temperature, 70 ℃ of lower isothermal reactions 2 hours.Stop at last stirring, leave standstill, with the supernatant liquid sucking-off, use hexane repetitive scrubbing three times, obtain catalyzer after the drying.
The vinyl polymerization test
2L stainless steel polymeric kettle is no less than three times with the high pure nitrogen displacement, then in polymeric kettle, add the 1.2L normal hexane, add the certain density triethyl aluminum of 4ml and 1.5mg solid catalyst, rising system temperature to 60 ℃ after open stirring, injecting ethene to system pressure is 0.6MPa, keeps temperature of reaction system, constant pressure, keeps 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 the kinetics of polymerization reaction curve is seen Fig. 1.
Embodiment 2
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 1 minute into by 2 minutes.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 3
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 5 minutes into by 2 minutes.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 4
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the time of hyperacoustic processing changed 8 minutes into by 2 minutes.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 5
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 30W into by 50W.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 6
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 80W into by 50W.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 7
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 150W into by 50W.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 8
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 20KHz into by 40KHz.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 9
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 30KHz into by 40KHz.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 60KHz into by 40KHz.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 11
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, hyperacoustic frequency changes 80KHz into by 40KHz.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 12
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of propyl carbinol changes 4ml into by 5ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 13
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of propyl carbinol changes 6ml into by 5ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 14
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of aluminium diethyl monochloride changes 25ml into by 30ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 15
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of aluminium diethyl monochloride changes 20ml into by 30ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 16
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of titanium tetrachloride changes 3ml into by 4ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Embodiment 17
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, the dosage of titanium tetrachloride changes 5ml into by 4ml.Carry out polymerization with this catalyst component with embodiment 1 identical method.It the results are shown in Table 1.
Comparative example 1
With the method Kaolinite Preparation of Catalyst component identical with embodiment 1, but in the Kaolinite Preparation of Catalyst process, do not use ultrasonic technology to process.The catalyzer dosage is that 10mg carries out polymerization with this catalyst component with embodiment 1 identical method during polyreaction.It the results are shown in Table 1.
Table 1, embodiment be table as a result
Claims (11)
1. 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 pure magnesium compound, and the add-on of alcohol is 0.1～6mol alcohol/1mol magnesium halide in the consumption of magnesium halide;
(2) pure magnesium compound and haloalkyl reactive aluminum form an intermediate product, and haloalkyl aluminium add-on is 0.5～3mol haloalkyl aluminium/1mol magnesium halide in the consumption of magnesium halide;
(3) utilize ultrasonic unit that the gained intermediate product is processed, employed ultrasonic unit power is 30～200W, and frequency is 20～100KHz;
(4) add the titanium compound reaction again and obtain catalyzer, the add-on of titanium compound is 2～5mol titanium tetrachloride/1mol magnesium halide in the consumption of magnesium halide.
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 the 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-mExpression, 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, R wherein
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 employed ultrasonic unit power is 40～150W, and frequency is 30～80KHz.
9. extra high-molecular polythene catalyst according to claim 8 is characterized in that 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.
10. method for preparing the described extra high-molecular polythene catalyst of one of claim 1-9 is characterized in that may further comprise the steps:
1) under the nitrogen protection, a certain amount of magnesium halide is put into container, add hydrocarbon solvent, container is placed oil bath, open and stir, add again alcohol, heat up, in 40～130 ℃ of lower stirrings, refluxed 0.5～3 hour;
2) slowly add haloalkyl aluminium and step 1) described in pure magnesium compound in 40～130 ℃ of lower stirrings, 0.5～1 hour formation intermediate product refluxes;
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 40～130 ℃ of lower stirrings after closing ultrasonic unit, refluxes 0.5～2 hour;
4) slowly add titanium compound, in 40～130 ℃ of lower stirrings, refluxed 1～3 hour;
5) stop to stir, left standstill 1～30 minute, treat granules of catalyst sedimentation, layering, with the supernatant liquid sucking-off, add hydrocarbon solvent washing solid particulate, so repetitive scrubbing makes catalyzer more after drying.
11. preparation method according to claim 12 is characterized in that described hydrocarbon solvent comprises aliphatic compound or compound fragrant hydrocarbon, is Skellysolve A, iso-pentane, hexane, heptane, octane, decane, benzene or toluene.
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| 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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| 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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| CN104558294A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Ultrahigh-molecular weight polyethylene catalyst and preparation method thereof |
| CN105658684A (en) * | 2014-02-13 | 2016-06-08 | 博里利斯股份公司 | Disentangled high or ultrahigh molecular weight polyethylene prepared with ziegler-natta catalyst |
| CN113185627A (en) * | 2021-05-20 | 2021-07-30 | 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 |
| CN116333193A (en) * | 2023-05-22 | 2023-06-27 | 上海优铖工逸技术有限公司 | Ziegler Natta catalyst, preparation method and application thereof |
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| CN105658684A (en) * | 2014-02-13 | 2016-06-08 | 博里利斯股份公司 | Disentangled high or ultrahigh molecular weight polyethylene prepared with ziegler-natta catalyst |
| CN113185627A (en) * | 2021-05-20 | 2021-07-30 | 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 |
| CN116333193A (en) * | 2023-05-22 | 2023-06-27 | 上海优铖工逸技术有限公司 | Ziegler Natta catalyst, 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 |
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