CN104356260A - Preparation method and application of supported chromium catalyst for olefin polymerization - Google Patents
Preparation method and application of supported chromium catalyst for olefin polymerization Download PDFInfo
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- CN104356260A CN104356260A CN201410658517.XA CN201410658517A CN104356260A CN 104356260 A CN104356260 A CN 104356260A CN 201410658517 A CN201410658517 A CN 201410658517A CN 104356260 A CN104356260 A CN 104356260A
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Abstract
The invention relates to a preparation method of a supported chromium catalyst for olefin polymerization, which comprises the following steps: (1) drying a supporter silica gel at 80-250 DEG C, wherein the pore volume of the supporter silica gel is 1.4-2.3 mL/g, and the specific area is 300-700 m<2>/g; (2) supporting a chromium compound on the supporter silica gel to obtain a catalyst supporter; and (3) calcining to activate the catalyst supporter in a non-reducing gas or vacuum at 500-1000 DEG C to obtain the supported chromium catalyst. The catalyst has the advantages of great potential of melt index (MI) and favorable MI response, can obtain wide molecular weight distribution while avoiding generating excessive low-molecular-weight products, and is suitable for producing high-melt-index polymers.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, relate to a kind of preparation method and application thereof of the supported chrome series catalysts for olefinic polymerization specifically.
Background technology
Polyethylene catalysts, through the development of many decades, defines the commercialized catalyst system based on Ziegler-Natta catalyst, chromium-based catalysts and metallocene catalyst.Chromium-based catalysts is commonly called Phillips catalyzer, and compared with other two classes catalyzer, obtained polyvinyl resin has wide molecular weight distribution, mainly for the production of the polyethylene of the purposes such as blowing, bucket packaging, tubing.The wide molecular weight distribution character of polyvinyl resin can increase its mobility in blow-molding process, improves the environmental stress cracking resistance of blow molded product, and reduces the crack velocity of tubing.Hydrogen due to chromium-based catalysts adjusts ability poor, has higher molecular weight and low melt index with the polyethylene that chromium-based catalysts is produced.People have done a lot of research, to improve the melting index of polymeric articles how improving in chromium-based catalysts hydrogen tune ability.Carrying out chemical modification to the active centre chromium of chromium/silica-gel catalyst or carrier is conventional raising melt index method.
The inorganic oxide of silicon oxide-containing contacts with magnesium compound by CN101081877A, prepare the cogelled of magnesium oxide and silicon-dioxide, roasting obtains the carrier silica gel of magnesium doping, then the ethene polymers of the catalyst preparing obtained after load chromium cpd can improve density and molecular weight distribution is broadened.But complex treatment process de-to carrier silicon in this patent, step of preparation process is loaded down with trivial details, and energy consumption is larger.Broaden by the molecular weight distribution of titanium component to the low molecular weight part of the polymkeric substance that catalyst modification also can make chromium-based catalysts produce, and improve melting index, but the molecular-weight average of polymkeric substance can be reduced.About titanium component add in chromium/silica-gel catalyst improve catalyzer hydrogen adjust ability have a lot of document or patent report, such as USP3887494, USP3119569, USP6201920 etc.At supported on carriers aluminum compound or add the character (such as, melt index) being also often used to improve olefin polymer containing aluminium auxiliary agent, as CN 101896508, US3984351, US2959577 etc.US3984351 discloses the method for deposition chromium compound and the postactivated Kaolinite Preparation of Catalyst of aluminum compound on inorganic carrier material.Then be combined with metallic reducing agent or nonmetallic reduction agent by the material obtained, thus be provided for the catalyst system of olefinic polymerization, its reductive agent is preferably the compound of boracic.Described silica xerogels is preferred solid support material.Described catalyzer is prepared by deposition chromium compound on inorganic carrier and aluminum compound.Described compound is organic compound, and sediment source is in the organic solvent of inertia.Catalyst system disclosed in this patent makes the character of olefin polymer obtain.But, these use other element usually to there is to active centre modification or the structurally-modified method of carrier hole the problem that complicated process of preparation, production cycle are longer or have greater environmental impacts, the lower molecular weight content of the polyvinyl resin of this kind of Catalyst Production is higher in addition, and material mechanical performance is influenced.Based on the variety of problems of prior art,
The invention provides a kind of olefin polymerization catalysis, compared with prior art there is following characteristics:
One, do not use other metallic element to active centre modification or support modification;
Two, polymericular weight is wide distribution, and low molecular weight part is controlled simultaneously;
Three, respond (HLM/MI ratio) with the polymeric shear of Catalyst Production of the present invention lower, be applicable to film and tubing that production requirement polymkeric substance has wide molecular weight distribution;
Four, with the polymkeric substance of Catalyst Production of the present invention, there is outstanding environmental stress cracking resistance.
Summary of the invention
One of the object of the invention is to provide a kind of supported chrome series catalysts for olefinic polymerization, and its preparation method.This catalyzer is without the need to other metallic element modification and have good melting index MI response.At the same reaction temperature, easier the avoiding when obtaining wide molecular weight distribution of this catalyzer produces too much low molecular weight product.Two of the object of the invention there is provided this supported chrome series catalysts application method in the polymerization.
A kind of supported chrome series catalysts for olefinic polymerization provided by the invention, its preparation method comprises the following steps:
(1) by carrier silica gel drying treatment at 80 ~ 250 DEG C;
(2) load chromium cpd in carrier silica gel, obtained support of the catalyst; ;
(3) by support of the catalyst calcining and activating in the non-reducing gas of 500 ~ 1000 DEG C or vacuum, the final catalyzer for polyreaction is obtained;
Wherein the order of step (1) and (2) to be exchanged.
Carrier silica gel described in step of the present invention (1) is with silica gel (Si0
2) as the inorganic carrier of major ingredient, this carrier is selected from catalysis level silica gel, silica gel-aluminum oxide (Al
20
3), silica gel-boron oxide (B
20
3), silica gel-titanium oxide (Ti0
2), silica gel-zirconium white (Zr0
2) in one or its mixture, wherein Si0
2silica gel content is in the carrier 80 ~ 100 % by weight, preferably 90 ~ 99 % by weight.
Carrier silica gel pore volume described in step of the present invention (1) is 1.4 ~ 2.3mL/g, and specific surface area is 200 ~ 600m
2/ g.The activity of specific surface area to final catalyzer of carrier silica gel has material impact.The hydrogen of catalyzer adjusts ability to increase along with the specific surface area of carrier silica gel and to reduce.General specific surface area is little, and polymerization activity can be caused on the low side.Therefore, in the present invention, the preferred specific surface area of carrier silica gel is 300 ~ 500m
2/ g's.Described carrier silica gel is pore volume 1.4 ~ 2.3mL/g.The activity of pore volume on final catalyzer of carrier silica gel also has impact, and the hydrogen of catalyzer adjusts ability can reduce and reduce by pore volume.But carrier silica gel is excessive must be prepared by solution extraction, cost is higher.The preferred pore volume of the present invention is the carrier silica gel of 1.5 ~ 1.8mL/g.
In step of the present invention (1), carrier silica gel can select median size to be the carrier silica gel of 30 ~ 300 μm, is preferably the carrier silica gel that median size is 70 ~ 130 μm.
Described in step of the present invention (1), carrier silica gel contains a small amount of sodium element.The too high hydrogen that can reduce catalyzer of sodium content adjusts ability, and therefore, in the present invention, the sodium content of carrier silica gel is less than 2500ppm, is preferably less than 1500ppm.
Want drying treatment to remove free-water before carrier silica gel activation treatment in step of the present invention (1).
Drying treatment can before load chromium cpd, also can after load chromium cpd.When the chromium cpd of load is water soluble ge cpd, drying treatment can after load chromium cpd; When the chromium cpd of load is for being dissolved in organic solvent, drying treatment need before load chromium cpd.Special, when organic solvent is easy volatile solvent, can moistly process.
Carrier silica gel described in step of the present invention (1) drying treatment 0.1 ~ 72h at 80 ~ 250 DEG C.
Carrier, when activating, may have impact to the pore structure of carrier, surface chemical property etc., so want drying treatment to remove free-water before support of the catalyst activation treatment.The temperature of drying treatment can be 80 ~ 250 DEG C, and be preferably 100 ~ 235 DEG C, the best is 150 ~ 225 DEG C.The drying treatment time is 0.1 ~ 72h, and be preferably 1 ~ 10 hour, the best is 2 ~ 8 hours.
In step of the present invention (1), drying treatment can adopt any method being easy to realize, and such as, in fluid bed heat facture, vacuum heat treatment method, open container, electrostatic is except water law, rotatory drier, and other known method any.Drying treatment can be carried out in dry air, in the gas such as nitrogen, hydrogen, carbon monoxide, also can carry out under vacuo.Preferred version for carry out in nitrogen.
Chromium cpd described in step of the present invention (2) is be selected from one or more mixtures in ammonium chromate, chromium acetate, chromium nitrate, chromium trioxide, two aromatic hydrocarbons chromium cpd, chromate and chromium complex.Described chromium cpd is water soluble ge cpd or the chromium cpd dissolving in organic solvent.Can be ammonium chromate, chromium acetate, chromium nitrate, chromium trioxide; Also can be two aromatic hydrocarbons chromium cpd, such as two phenyl chromium; Also comprise chromate class, such as di-t-butyl chromate; And chromium complex, such as acetylacetonate chromium.
In step of the present invention (2), the load of chromium cpd is that chromium cpd and carrier silica gel are carried out sufficient impregnation, then dry.Chromium cpd in the present invention can load formerly in the carrier silica gel of drying treatment, also first Yu without drying treatment carrier silica gel can react, then carry out drying treatment.For water soluble ge cpd, before load chromium cpd, silica gel need not drying treatment.And being dissolved in the chromium cpd of organic solvent, carrier silica gel can first through drying treatment or without drying treatment.For the chromium cpd being dissolved in organic solvent, preferred version is for carry out drying treatment to carrier silica gel.
In step of the present invention (2), the consumption of chromium cpd must ensure there is enough chromium content in final catalyzer (after calcining), chromium content in final catalyzer is 0.001 ~ 10 % by weight, preferably 0.1 ~ 5 % by weight, most preferably 0.5 ~ 1.5 % by weight.
By catalyst precursors calcining and activating in the non-reducing gas of 500 ~ 1000 DEG C or vacuum in step of the present invention (3), obtain the final catalyzer for polyreaction;
Non-reducing gas described in step of the present invention (3) is air, oxygen, nitrogen or carbonic acid gas.
The calcining and activating time of the catalyst precursors described in step of the present invention (3) is 0.5 ~ 24 hour.The support of the catalyst be made up of chromium cpd and carrier silica gel all will by activation could form final catalyzer and for be polymerized.Reactivation process carries out high-temperature calcination under non-reducing gas air atmosphere, and calcining temperature is 500 ~ 1000 DEG C, is preferably 550 ~ 800 DEG C, most preferably is 600 ~ 750 DEG C.The soak time of support of the catalyst is 0.5 ~ 24 hour.
In final obtained supported chrome series catalysts described in step of the present invention (3), the weight percentage of chromium is 0.1 ~ 5 % by weight.
The application of the supported chrome series catalysts for olefinic polymerization described in the present invention, its feature is the homopolymerization of this catalyzer for ethene, or the copolyreaction of ethene and the aliphatics list a-alkene containing 3 ~ 10 carbon atoms and/or the conjugated diolefine containing 4 ~ 10 carbon atoms, when polymerization temperature is greater than 100 DEG C, the melt flow ratio HLMI/MI ratio of the polymkeric substance of preparation is less than 100.
The catalyzer prepared according to the inventive method may be used for the polymerization of silt oar and loop technology slurry polymerization (Particle FormProcess).Polymerization is carried out usually in the inert diluent of drying, and this thinner can be Trimethylmethane, positive penta protective embankment, methyl cyclohexanol and benzene etc.Polymeric reaction temperature is 60 ~ 110 DEG C, and polymerization pressure is 1.7 ~ 4.1MPa.Polymkeric substance processes with carbonic acid gas or water usually, object is to make residual catalyst inactivation, also use oxidation inhibitor to improve performance simultaneously, as Yoshinox BHT (BHT), then use ordinary method carry out drying and obtain last polymerization product.As known technology, hydrogen can be used in the polymerization to control the molecular weight of polymkeric substance.Polymerization intermittently can be carried out at stirring reactor, also can carry out continuously in a loop reactor, or carry out in continuous print multiple reactor.Catalyzer of the present invention also can be applicable to the polymerization technique of solution method, vapor phase process or other routines, but catalyzer of the present invention is used for slurry process than the polymkeric substance more can produced for other technique compared with high fusion index.
Catalyzer of the present invention is applicable to the ethylene copolymer produced common solid vinyl homopolymer and account for leading market status.As comonomer can be the aliphatic mono-alpha olefins containing 3 ~ 10 carbon atoms, such as propylene, l-butylene, l-amylene, l-hexene, l-octene etc., also can be the conjugated diolefine containing 4 ~ 10 carbon atoms.Ethene can carry out copolyreaction with above-mentioned one or more comonomer, and wherein vinyl monomer is major portion, and other comonomer can with ethene with any ratio copolymerization.Therefore in copolyreaction, vinyl monomer accounts for 93 ~ 99.6 % by weight, and rest part is higher alkene comonomer, and in the ethylene copolymer obtained like this, ethylene moiety content is 97 ~ 99.6 % by weight.In wider range of application, ethylene copolymer can be prepared with the comonomer of vinyl monomer and 0.2 ~ 20 % by weight of 80 ~ 99.8 % by weight.
The polymer phase ratio prepared under similar polymerizing condition to the chrome catalysts of prior art, uses the polymkeric substance of Catalyst Production of the present invention to have lower HLMI/MI ratio.This characteristic demonstrates superiority when producing tubing and film.In the present invention, polymerization temperature is greater than polymer melt starting temperature IO, and (the HLMI/MI ratio of the polymkeric substance prepared during TC is less than 100, is preferably less than 90, is more preferably less than 80, best for being less than 70.In a word, HLMI/MI is than lower, and this superiority can be more outstanding.Certainly, HLMI/MI is than relevant with polymeric reaction condition, and particularly polymerization temperature, if polymerization temperature reduces, this ratio can raise.
Accompanying drawing explanation
Fig. 1 is the weight-average molecular weight scatter chart of polymkeric substance that the catalyzer prepared of Application Example 4 and Comparison study sample catalyzer obtain.
Embodiment
Set forth the present invention further below by the detailed description of specific embodiments of the invention, but the present invention is not limited to these embodiments.
Unless otherwise indicated, polyreaction evaluation in embodiment is carried out as follows: polyreaction evaluation is carried out in 4 liters of stainless steel cauldrons with whipping appts, mixing speed is 1000rpm, reactor has stainless steel chuck, containing cooling fluid in chuck, the temperature of cooling fluid is controlled by heat exchanger, assists and temperature of reaction can be made to be accurate to l DEG C with electronic temperature control device.
First under nitrogen protection a small amount of solid catalyst (usual 0.01 ~ 0.1g) is joined in dry reactor; then the Trimethylmethane of 1200g is added; heating makes temperature of reaction be elevated to design temperature; usually at about 105 DEG C; finally pass into the reaction pressure of ethene to setting; usually at 3.7MPa, pass into ethene continuously, in whole polyreaction evaluation procedure, maintain this reaction pressure.According to test requirements document continuously stirring reaction certain hour, be generally 1 hour.The polymerization activity situation of catalyzer can be understood by recording the ethene cumulative amount passing into reactive system.
After reaction terminates, cut off ethene rapidly, after the slow pressure release of reactor, reclaim polymer powders.The residue that may exist in reactor, knot wall thing etc. must be cleaned out, in order to avoid affect the accuracy of polyreaction evaluation next time.Weigh after polymer powders drying.The polymerization activity polymer material weight (g polyethylene/g catalyzer h) of every gram of Catalyst Production per hour represents.In embodiment, the performance index of each polymkeric substance measure as follows
Melting index (MI) measures: according to standard A STM D1238 conditional 190/2, at 190 DEG C, measure with 2.16kg counterweight.Unit is g/10min.
High load melt index (HLMI) measures: according to standard A STM D1238 conditional 190/2.16, measures at 190 DEG C with 21.6kg counterweight.Unit is g/10min.
Density polymer measures: measure according to standard A STM D1505-68 and ASTM D1928 Program C.Polymer melt rear mold compacting sample, sample with the cooling of the speed of 15 DEG C/h, and measures deposit about 40h under room temperature state after.With the polymer weight (g/cm of every cubic centimetre
3) represent.
Environmental stress cracking resistance (ESCR) measures: measure according to standard A STM D1693 conditional B.Unit is h.
EXAMPLE l:
Catalyst preparing adopts carrier silica gel A, and pore volume is 1.70mL/g, and specific surface area is 371m
2/ g, aperture is
sodium content is 1000ppm.The ethanolic soln of these carrier silica gel chromium acetates is flooded, is warming up to 50 DEG C and keeps 2h, at 90 DEG C, use nitrogen purging evaporate to dryness, obtain support of the catalyst.By the support of the catalyst that formed at 815 DEG C with fluidization air calcining and activating 3 hours, obtain final catalyzer.Carry out specific surface to final catalyzer and pore structure study draws, specific surface area of catalyst is 339m
2/ g, pore volume 1.61mL/g, aperture
in final catalyzer, chromium percentage composition is l % by weight.Catalyzer is carried out vinyl polymerization evaluation at 108 DEG C, and polymerization activity is 5300g polyethylene/g catalyzer, and melt index is 1.28g/10min.The contrast sample catalyzer of the chromium aluminum compound load simultaneously of Pq Corp. of the U.S. being produced activates and polyreaction evaluation under similarity condition, and polymerization activity is 5100g polyethylene/g, and melting index is 1.35g/10min.Prove that the present embodiment prepared catalyst has higher activity and close melting index level when not containing aluminium element modification.
Embodiment 2:
In the same manner as in Example 1, but the activation temperature of support of the catalyst is adjusted to 843 DEG C, catalyzed ethylene and 1-hervene copolymer.Target setting density polymer is 0.955g/mL, and target produces HIC hollow blow molding level polyethylene.Catalyzed ethylene and 1-hervene copolymer.Polymerization activity is 7000g polyethylene/g catalyzer, and melt index is 0.58g/10min.Activated under similarity condition and polyreaction evaluation by the contrast sample catalyzer that Pq Corp. of the U.S. produces equally, polymerization activity is 6800g polyethylene/g, and melting index is 0.60g/10min.Prove that this patent prepared catalyst has higher activity and close melting index level when not containing aluminium element modification.
Embodiment 3:
In the same manner as in Example 1, but the activation temperature of support of the catalyst is adjusted to 705 DEG C, catalyzed ethylene and 1-hervene copolymer.Target setting melt index is 0.58g/10min, and target produces tube material and mould material using polythene.Required polymeric reaction temperature should be 103.8 DEG C, and 1-hexene add-on is 5.3mL.Now polymerization activity is 5730g polyethylene/g catalyzer, and density polymer is 0.952g/mL, and polymkeric substance HLMI/MI ratio is 69, and die swelling ratio is 81.Equally the contrast sample catalyzer that Pq Corp. of the U.S. produces is activated and polyreaction evaluation under similarity condition, required polymeric reaction temperature should be 103.5 DEG C, 1-hexene add-on is 5.2mL, polymerization activity is 5490g polyethylene/g catalyzer, polymkeric substance HLMI/MI ratio is 66, and die swelling ratio is 79.Prove that this patent prepared catalyst has higher activity, close temperature of reaction and HLMI/MI ratio when not containing aluminium element modification.
Embodiment 4:
In the same manner as in Example 1, but the activation temperature of support of the catalyst is adjusted to 677 DEG C, polyreaction greenhouse is adjusted to 105 DEG C.Activated under similarity condition and polyreaction evaluation by the contrast sample catalyzer that Pq Corp. of the U.S. produces equally, the weight-average molecular weight distribution curve of polymkeric substance is shown in accompanying drawing 1.Can find out, basically identical with the weight-average molecular weight distribution curve of the contrast sample of chromium aluminium load without other metal-modified embodiment 4, but the weight-average molecular weight of the polymkeric substance of embodiment 4 preparation is slightly higher than the product of the catalysis of contrast sample.Concrete rheological property contrast is as shown in table 1 below.
Table 1
In table, Eta (0) is zero-shear viscosity, and Tau is the relaxation time, CY ?a be rheological breadth parameter, MI is melting index, and HLMI is high load melt index,
eta@0.1for low shear rate (0.1 revolutions per second) viscosity, Eta@100 is high shear rate (100 revolutions per seconds) viscosity,
tanD@0.1for storage modulus loss during rotating speed 0.1 revolutions per second, storage modulus loss when TanD@100 is rotating speed 100 revolutions per seconds;
Data from table, zero-shear viscosity (Eta (0)) a little higher than contrast sample in embodiment 4, this may be owing to implementing the slightly little cause of mean pore size in 4 examples.Commercially produce in application, this species diversity can be made up by adjustment melt index.And other data, as MI and HLMI etc., embodiment 4 and contrast sample are more or less the same, and have similar rheological property both proving.Also prove not use in this patent the performance that the catalyzer of other metallic element modification can realize with metal-modified catalyzer, save cost, process simplification.
Embodiment 5:
In the same manner as in Example 1, but weight of chromium per-cent in final catalyzer is adjusted to 1.09%, catalyzed ethylene polymerization, polymerization activity is 5520g polyethylene/g, and melting index is 0.98g/10min.
Embodiment 6:
In the same manner as in Example 1, but chromium cpd is replaced with chromium acetylacetonate, the solvent of dipping replaces with normal heptane by ethanol.Support of the catalyst activation temperature is 843 DEG C, controls 0.89% by weight of chromium per-cent in final catalyzer, catalyzed ethylene and 1-hervene copolymer, and polymerization temperature is 103 DEG C, and final polymerization activity is 6900g polyethylene/g, and melting index is 0.59g/10min.
Embodiment 7:
In the same manner as in Example 1, but the solvent of dipping is replaced with water by ethanol, in final catalyzer, weight of chromium per-cent is l%, catalyzed ethylene and 1-hervene copolymer.Activation temperature 705 DEG C, subject polymer density is 0.952g/mL.Then required polymeric reaction temperature should be 104.1 DEG C, and 1-hexene add-on is 5.5mL.Now polymerization activity is 5950g polyethylene/g catalyzer, and polymkeric substance HLMI/MI ratio is 75, and die swelling ratio is 85.
Claims (10)
1., for a preparation method for the supported chrome series catalysts of olefinic polymerization, it is characterized in that the method comprises the steps:
(1) by carrier silica gel drying treatment at 80 ~ 250 DEG C;
(2) load chromium cpd in carrier silica gel, obtained support of the catalyst;
(3) by support of the catalyst calcining and activating in the non-reducing gas of 500 ~ 1000 DEG C or vacuum, the final catalyzer for polyreaction is obtained;
Wherein the order of step (1) and (2) to be exchanged.
2. the preparation method of catalyzer according to claim 1, is characterized in that, the carrier silica gel described in step (1) is with Si0
2silica gel is as the inorganic carrier of major ingredient, and this carrier is selected from one in catalysis level silica gel, silica gel-aluminum oxide, silica gel-boron oxide, silica gel-titanium oxide, silica gel-zirconium white or its mixture, wherein Si0
2silica gel content is in the carrier 80 ~ 100 % by weight.
3. the preparation method of catalyzer according to claim 1, is characterized in that, in described step (1), carrier silica gel pore volume is 1.4 ~ 2.3mL/g, and specific surface area is 200 ~ 600m
2/ g.
4. the preparation method of catalyzer according to claim 1, is characterized in that, in carrier silica gel described in step (1), sodium content is less than 1500ppm.
5. the preparation method of catalyzer according to claim 1, is characterized in that, carrier silica gel drying treatment 0.1 ~ 72h at 80 ~ 250 DEG C in step (1).
6. the preparation method of catalyzer according to claim 1, it is characterized in that, chromium cpd described in step (2) is be selected from one or more mixtures in ammonium chromate, chromium acetate, chromium nitrate, chromium trioxide, two aromatic hydrocarbons chromium cpd, chromate and chromium complex.
7. the preparation method of catalyzer according to claim 1, is characterized in that, in described step (3), non-reducing gas is air, oxygen, nitrogen or carbonic acid gas.
8. the preparation method of catalyzer according to claim 1, is characterized in that, in step (3), the calcining and activating time of catalyst precursors is 0.5 ~ 24 hour.
9. the preparation method of catalyzer according to claim 1, is characterized in that, in step (3), in final obtained supported chrome series catalysts, the weight percentage of chromium is 0.1 ~ 5 % by weight.
10. the application of the supported chrome series catalysts for olefinic polymerization described in a claim l, it is characterized in that, this catalyzer is used for the homopolymerization of ethene, or the copolyreaction of ethene and the aliphatics list a-alkene containing 3 ~ 10 carbon atoms and/or the conjugated diolefine containing 4 ~ 10 carbon atoms, when polymerization temperature is greater than 100 DEG C, the melt flow ratio HLMI/MI ratio of the polymkeric substance of preparation is less than 100.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690151A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
| CN116217760A (en) * | 2018-09-17 | 2023-06-06 | 切弗朗菲利浦化学公司 | Photo-treatment of chromium catalysts and related catalyst preparation systems and polymerization processes |
-
2014
- 2014-11-18 CN CN201410658517.XA patent/CN104356260A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690151A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
| CN108690151B (en) * | 2017-04-07 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
| CN116217760A (en) * | 2018-09-17 | 2023-06-06 | 切弗朗菲利浦化学公司 | Photo-treatment of chromium catalysts and related catalyst preparation systems and polymerization processes |
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Application publication date: 20150218 |