CN106749786A - A kind of polyethylene catalysts - Google Patents
A kind of polyethylene catalysts Download PDFInfo
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- CN106749786A CN106749786A CN201610572047.4A CN201610572047A CN106749786A CN 106749786 A CN106749786 A CN 106749786A CN 201610572047 A CN201610572047 A CN 201610572047A CN 106749786 A CN106749786 A CN 106749786A
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- catalyst
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- polyethylene catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
The present invention is a kind of polyethylene catalysts.Including main body active catalyst, inorganic oxide carrier, modifying agent and co-catalyst, main body active catalyst is chromic salts described in wherein A., and its content in catalyst gross mass is 0.5 3%；B. the carrier is that the technical requirements of inorganic oxide are：A. surface area is about 300 600m2/g；B. pore volume is about 1 3cc/g；C. aperture is about 100 500；D. particle size is about 50 150 μm；C. the modifying agent is to prepare alkyl silane chromate ester catalyst recovered liquid；D. the co-catalyst is the alkyl compound of aluminium, lithium, boron, zinc.Catalyst of the invention, adjusts the performances such as susceptibility to have clear improvement in polyvinyl resin product molecular weight distribution, copolymerization performance, hydrogen.
Description
Technical field
The present invention is a kind of polyethylene catalysts.More particularly to support type Organic Chromium catalyst for ethylene polymerization.
Background technology
Chromium-based catalysts are applied in the production of polyethylene earliest as an important kind of ethylene rolymerization catalyst.
From initial in silica gel (SiO2) or silica gel-aluminum oxide (SiO2-Al2O3) on supported chromium research success so far,
It has been discovered that the activation method after the preparation method of silica gel and load chromium-based catalysts can change the average molecular matter of product
Amount (hereinafter referred to as molecular weight).Supported chrome series catalysts are had been widely used in solwution method, slurry process, vapor phase method PE productions
In technique.PE resins obtained in chromium-based catalysts can be made in the hollow molding such as bottle, tank field shape it is more complicated, processing rotation
Turning property is preferable, cut bad mouth melts the thicker product in part, and this is because the resin contains long-chain branch component and a small amount of supra polymer
Amount (about 107) component, so that its processing characteristics is more superior.
In PE production processes, induction time is long, product melt index is low, copolymerizable due to existing for traditional chromium oxide catalyst
The shortcomings of energy is poor, hydrogen adjusts insensitive, thus can not increasingly meet requirement of the people to products made thereby performance in application.Therefore,
In 20 century 70 mid-terms, the chemical company such as UCC, Phillips is actively improved to chromium-based catalysts.
USP2, supported chromium oxide catalyst disclosed in 825,721, be chromium trioxide or under high temperature oxidizing conditions extremely
Few energy partial oxidation loads to what is prepared on silica gel in aqueous into the compound of chromium trioxide.This catalyst overcomes
The complicated shortcoming of active component synthesis technique, reduces catalyst cost, but with the product molecular weight distribution of the catalyst preparation
It is narrower.
USP3, support type silane chromate ester catalyst disclosed in 324,095, carrier is inorganic oxide, and active component is
Silane chromate ester, co-catalyst is a kind of organic calorize of the alkoxy being connected in at least one or no more than 2 in aluminium atom
Compound；Although the catalyst can be used to prepare the extrusion molding level product that molecular weight is higher, molecular weight distribution is wider, but this catalyst
The synthesis technique of active component is complicated, makes catalyst expensive.
The polyethylene catalysts prepared by chromium oxide have high activity, certain induction time, can produce with macromolecule
Amount and the polymer of intermediate molecular weight distribution.Catalyst activity based on silyl chromate is relatively low, but can produce wider point
The polymer of son amount distribution.Silylchromate catalysts production cost is generally higher compared with chromium oxide catalyst price.
The content of the invention
It is an object of the invention to avoid above-mentioned weak point of the prior art, and when providing a kind of activity high, induction
Between polyethylene product suitable, suitable for producing range of molecular weight distributions wider catalyst.
The purpose of the present invention can be reached by following measure：
Polyethylene catalysts of the invention, including main body active catalyst, inorganic oxide carrier, modifying agent and co-catalyst,
Wherein：
A. the main body active catalyst is chromic salts, and its content in catalyst gross mass is 0.5-3%
Carrier described in B is that the technical requirements of inorganic oxide are：
A. surface area is about 300-600m2/g；
B. pore volume is about 1-3cc/g；
C. aperture is about 100-500；
D. particle size is about 50-150 μm；
C. the modifying agent is to prepare alkyl silane chromate ester catalyst recovered liquid；
D. the co-catalyst is the alkyl compound of aluminium, lithium, boron, zinc.
The chromic salts is selected from oxide, acetate, carboxylate, bichromate, the chromate of chromium.Can be a kind of or a kind of
Above organic or inorganic chromic salts, the wherein oxidation state of chromium are 0-6.Chromic salts in the present invention also includes crome metal.Typically, chromium
The chemical formula of salt is CrXn, and X can be able to be any organic or inorganic group with can be different in formula, and n is integer, and its value is 1-6.
Typical organic group, each group can contain about 1-20 carbon atom, can be alkyl alkoxy, ester group, ketone group and/or acid amides
Base.Organic group can be：Straight chain base or the base containing side chain, cyclic group or acyclic radical, aryl or aliphatic group, and can be by the fat that mixes
Race's base, aryl and/or cycloaliphatic radical are constituted.Typical inorganic chromium compound has：The acetate of chromium, bichromate, chromate, chromium
Nitrate and chromium oxide etc..The vinegar of the oxide of the acetate of preferred chromium, the nitrate of chromium and chromium, more preferably chromium
Hydrochlorate.
The modifying agent is that alkyl silane chromate loads to the catalyst recovery produced on inorganic metal oxide support
Liquid.Modifying agent main component is alkylsilanol and unreactive hydrocarbons solvent.Alkylsilanol structural formula is R3SiOH.Wherein, R represents alkyl
Alkyl in silanol, alkyl may be the same or different, and should have 1-14 carbon atom.Alkylsilanol can be wrapped in the present invention
Include but be not limited to trimethyl silicane alkanol, triethyl silicane alcohol, tributyl silanol, triisopentyl silanol, three -2- ethylhexyls
Silanol, three decyl silanols, three（14）Base silane alcohol, tribenzyl silanol, triphen ethylsilane alcohol, triphenyl silanol,
Trimethylphenyl silanol etc., particularly preferred triphenyl silanol.Alkylsilanol solution concentration is 1 × 10-6- 100mol/L, preferably 1 ×
10-5- 10mol/L, more preferably 1 × 10-4-1mol/L。
The co-catalyst is alkyl organometallic compounds, and alkyl metal cpd can be the alkane of aluminium, lithium, boron, zinc
Based compound, preferred alkyl aluminum compound in the present invention.
Adoptable organo-aluminum compound is alkyl aluminum compound and alkoxy aluminum compound, and alkyl aluminum compound has：Three
Alkyl aluminum compound, aluminum alkyl halide and alkyl aluminum hydride.Generally, the alkyl of alkyl aluminum can with identical also different, and
And should have 1-14 carbon atom, and halogen is then fluorine, chlorine, bromine and iodine.Specific alkyl aluminum compound is included but is not limited to, and three
Aluminium methyl, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, two
Butyl aluminium bromide and close compound.Generally, alkoxy aluminum compound has general formula R2- Al-OR, wherein alkyl can be with identical
Also can be different, and should have 1-14 carbon atom, the example is included but is not limited to, diethylaluminium ethoxide, methoxyl group two
Aluminium ethide, ethyoxyl dimethyl aluminium, ethyoxyl diisopropyl aluminium, propoxyl group diethyl aluminum, ethyoxyl diisobutyl aluminum and ethoxy
Ylmethyl aluminium ethide.Triethyl aluminum is selected in embodiment, it should be appreciated that do not limited of the invention so.
The purpose of the present invention can also be reached by following measure：
Polyethylene catalysts of the invention, it is characterised in that
A. the main body active catalyst is chromic salts, and its content in catalyst gross mass is 0.6-1.5%
Carrier described in B is that the technical requirements of inorganic oxide are：
A. surface area is about 245-500m2/g；
B. pore volume is about 1.5-3cc/g；
C. aperture is about 100-300；
D. particle size is about 60-120 μm；
C. the modifying agent is that alkyl silane chromate loads to the recovered liquid produced during catalyst carrier；
D. the co-catalyst can be the alkyl compound of aluminium, lithium, boron, zinc.
Polyethylene catalysts of the invention, inorganic oxide carrier described in B is from silica gel, aluminum oxide, aluminum phosphate, oxygen
Any one chosen in change titanium, or its any two or more combination.
Polyethylene catalysts of the invention, the active ingredient of modifying agent described in C is alkylsilanol.
Polyethylene catalysts of the invention, metallic element and main body active catalyst chromium in co-catalyst described in D
Mol ratio is 0.1-50.
Polyethylene catalysts of the invention, co-catalyst described in D can be added to catalyst before polymerization catalyst reaction
In, also can be in polymerization process be added to polymerization system on the spot.
Technical scheme disclosed in polyethylene catalysts of the invention, there is following good effect compared to existing technology：
1. a kind of activity height, induction time polyethylene product suitably, suitable for producing range of molecular weight distributions wider are provided
The organic chrome catalysts of ethylene polymerization.
2. catalyst of the present invention is with respect to chromium oxide catalyst, polyvinyl resin product molecular weight distribution, copolymerization performance,
Hydrogen adjusts the performances such as susceptibility to have clear improvement.
Specific embodiment
The present invention will now be described in further detail by the embodiment：
Embodiment 1
The chromic acetate aqueous solution 0.87g that concentration is 50wt% is weighed, its chromium content is 11.5wt%, adds deionized water 56ml.Will
The chromic acetate aqueous solution for preparing is added in the silica gel of 20g Davison 955, is impregnated 6 hours after mixing, then in air gas
Dried more than 12 hours for 60-120 DEG C in atmosphere.Then the bottom that dried catalyst Precursors are put into 30 × 500mm of Φ is welded with
The quartz ampoule activator of sintered quartz distribution grid, be passed through makes catalyst fluidization through the high pure nitrogen of dehydration and deoxidation.Heat up heating stone
English pipe activator, maintains 2 hours at 200 DEG C, catalyst is further removed moisture, is warming up to 325 DEG C, switches to the dry of dehydration
Dry air, is warming up to 600 DEG C, maintains 4 hours, finally switchback high pure nitrogen again, and device to be activated is cooled to room temperature, takes out oxidation
Chrome catalysts are placed in nitrogen atmosphere and store for future use.Take 1g chromium oxide catalysts to be placed in catalyst preparation bottle, add TPS concentration
It is 3.84 × 10-3The PS modifying agent 12.5ml of mol/L, 45 DEG C of lucifuges are reacted 2.5 hours.Triethyl aluminum is added by Al/Cr=20,
Stirring 1 hour, then blows down solvent with High Purity Nitrogen, is made chromium content 0.5wt%, Al/Cr=20, TPS: Cr=0.5（Mol ratio）
PS0.5 catalyst.
Embodiment 2-5
Embodiment 2-5 is similar to the process of embodiment 1, and difference is different PS modifying agent dosage.In embodiment 2, PS modifying agent adds
Amount 25ml, TPS: Cr=1.0；In embodiment 3, PS modifying agent dosages 18.75ml, TPS: Cr=1.5；In embodiment 4, PS
Modifying agent dosage 25ml, TPS: Cr=2.0；In embodiment 5, PS modifying agent 20.83ml, TPS: Cr=3.0.
Comparative example 1
The silica gel 20g of Davidson 955 are taken, the bottom for being put into 30 × 500mm of Φ is welded with the quartz ampoule activation of sintered quartz distribution grid
Device, be passed through makes catalyst fluidization through the high pure nitrogen of dehydration and deoxidation.Intensification heated quarty tube activator is small in 200 DEG C of maintenances 2
When, catalyst is further removed moisture, it is continuously heating to 600 DEG C, maintain 4 hours, then device to be activated is cooled to room temperature, takes
Go out 955 silica gel for having activated and be placed in nitrogen atmosphere to store for future use.The 955 silica gel 1g that taking-up has been activated, are placed in catalyst preparation
In bottle, 30ml isopentane is added, be warming up to 45 DEG C, plus it is double（Tri-phenyl-silane）Chromate 0.06g, lucifuge is reacted 2.5 hours.Press
Al/Cr=20 adds triethyl aluminum, stirs 1 hour, then blows down solvent with High Purity Nitrogen, is made chromium content 0.5wt%, Al/Cr=20
It is double（Tri-phenyl-silane）Chromate（BC）Catalyst.
Polymerization evaluation is carried out to embodiment 1-5, comparative example 1, experimental result is shown in Table 1,2：
The polymerizing condition of table 1：85 DEG C, pressure：Normal pressure, polymerization time：1 hour
| Embodiment is numbered | Catalyst | Modifying agent（ml） | Co-catalyst | Al/Cr | Activity（gPE/gcat.h） |
| Embodiment 1 | PS0.5 | 12.5 | TEA | 20 | 3.61 |
| Embodiment 2 | PS1.0 | 25 | TEA | 20 | 2.48 |
| Embodiment 3 | PS1.5 | 18.75 | TEA | 20 | 2.39 |
| Embodiment 4 | PS2.0 | 25 | TEA | 20 | 2.02 |
| Embodiment 5 | PS3.0 | 20.83 | TEA | 20 | 1.99 |
Explanation：
Modifier concentration 3.84 × 10 in embodiment 1,2-3mol/L；
Modifier concentration 7.68 × 10 in embodiment 3,4-3mol/L；
Modifier concentration 1.15 × 10 in embodiment 5-2mol/L。
The polymerizing condition of table 2：85 DEG C, pressure：Normal pressure, polymerization time：1 hour
| Catalyst | Co-catalyst | Al/Cr | Viscosity average molecular weigh (x104) | |
| Embodiment 3 | PS1.5 | TEA | 20 | 30.92 |
| Comparative example 1 | BC CAT | TEA | 20 | 33.13 |
Claims (6)
1. a kind of polyethylene catalysts, it is characterised in that including main body active catalyst, inorganic oxide carrier, modifying agent and
Co-catalyst, wherein：
A. the main body active catalyst is chromic salts, and its content in catalyst gross mass is 0.5-3%
B. the carrier is that the technical requirements of inorganic oxide are：
A. surface area is about 300-600m2/g；
B. pore volume is about 1-3cc/g；
C. aperture is about 100-500；
D. particle size is about 50-150 μm；
C. the modifying agent is to prepare alkyl silane chromate ester catalyst recovered liquid；
D. the co-catalyst is the alkyl compound of aluminium, lithium, boron, zinc.
2. according to the polyethylene catalysts of claim 1, it is characterised in that
A. the main body active catalyst is chromic salts, and its content in catalyst gross mass is 0.6-1.5%
B. the carrier is that the technical requirements of inorganic oxide are：
A. surface area is about 245-500m2/g；
B. pore volume is about 1.5-3cc/g；
C. aperture is about 100-300；
D. particle size is about 60-120 μm；
C. the modifying agent is that alkyl silane chromate loads to the recovered liquid produced during catalyst carrier；
D. the co-catalyst can be the alkyl compound of aluminium, lithium, boron, zinc.
3. according to the polyethylene catalysts of claim 1, it is characterised in that inorganic oxide carrier described in B is from silica gel, oxygen
Any one chosen in change aluminium, aluminum phosphate, titanium oxide, or its any two or more combination.
4. according to the polyethylene catalysts of claim 1, it is characterised in that the active ingredient of modifying agent described in C is alkyl silicon
Alcohol.
5. according to the polyethylene catalysts of claim 1, it is characterised in that metallic element is lived with main body in co-catalyst described in D
Property catalyst chromium elemental mole ratios be 0.1-50.
6. according to the polyethylene catalysts of claim 1, it is characterised in that co-catalyst described in D can react in polymerization catalyst
Before be added in catalyst, also can be in polymerization process be added to polymerization system on the spot.
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| CN201610572047.4A CN106749786A (en) | 2016-07-20 | 2016-07-20 | A kind of polyethylene catalysts |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536767A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Supported chromium-based polyethylene catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453154A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Organic chromium catalyst for ethylene polymerization and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453154A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Organic chromium catalyst for ethylene polymerization and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536767A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Supported chromium-based polyethylene catalyst and preparation method thereof |
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