CN101519464B - Catalyst for vinyl polymerization or copolymerization as well as preparation and application thereof - Google Patents
Catalyst for vinyl polymerization or copolymerization as well as preparation and application thereof Download PDFInfo
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- CN101519464B CN101519464B CN2009100484742A CN200910048474A CN101519464B CN 101519464 B CN101519464 B CN 101519464B CN 2009100484742 A CN2009100484742 A CN 2009100484742A CN 200910048474 A CN200910048474 A CN 200910048474A CN 101519464 B CN101519464 B CN 101519464B
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Abstract
The invention relates to a catalyst for alkene, in particular a catalyst for vinyl polymerization or copolymerization and a method for preparing the catalyst and application of the catalyst. A carrierobtained through the treatment on anhydrous magnesium compound by an alcohol compound is added with at least one activator composition, at least one reagent for an electron compound and a titanium co ntent control element in the catalyst and at least one titanium composition to prepare the catalyst. The catalyst can be used for vinyl homopolymerization or copolymerization reaction between vinyl and other alkenes.
Description
Technical field
The present invention relates to a kind ofly be used for the particularly catalyzer of vinyl polymerization or copolymerization of alkene, and this Preparation of catalysts method and purposes.
Background technology
The existing ethylene polymerization catalysts that is used for, adopt with magnesium, titanium, halogen and electron donor mostly as basic catalyst component, for particle form and the size-grade distribution that guarantees catalyzer, usually above-mentioned catalyzer basal component is carried on the carriers such as inorganic magnesium compound, silica gel.In patents such as US302565, US4379759, CN1064870A, all be titanium compound, magnesium compound and electron donor to be loaded on the carriers such as inorganic magnesium compound, silica gel, because the distribution of particle sizes of carrier itself is inhomogeneous, the uniform distribution of control catalyst effective constituent on support of the catalyst be difficulty relatively, repetition stability in the catalyst preparation process is poor, and the particle form and the size distribution of resulting polymers are unsatisfactory.
US4376062 is on the basis of above-mentioned catalyst activity component, with the silicon-dioxide of smoke-like as carrier, mix with the parent of titanium compound, magnesium compound and electron donor compound, prepare catalyzer by spray-dired method, after this catalyzer is used for the ethene gas-phase fluidized bed polymerization process, the particle diameter of gained catalyzer and the particle form of polymkeric substance are easy to control, but the efficient of catalyzer is not too satisfactory, is not suitable for industrial production.
US501372 and US5081090 form homogeneous phase solution with alkoxyl magnesium and carbon dioxide reaction, low temperature and halide reagent reaction generate magnesium halide carrier, perhaps when generating magnesium halide carrier, carry titanium and generate solid catalyst, in the method for this patent statement, catalyst form is wayward, the synthetic polymer morphology is poor, and apparent density is little, is unfavorable for industrial production.
Summary of the invention
Order of the present invention has provided a kind of improved catalyzer that is used for vinyl polymerization or copolymerization, by in the anhydrous magnesium compound, adding organic oxygen-containing compound as reagent treatment, add organo-aluminium compound as activating reagent, and add ester compound therein as electron donor and titanium elements content control reagent, add titanium compound at last and carry out load, improve the gained catalyzer catalytic efficiency, improve the particle form of catalyzer.
The invention provides a kind of catalyzer that is used for vinyl polymerization or copolymerization, its main ingredient is: handling on the carrier of anhydrous magnesium compound gained with alkylol cpd, add at least a activator component, at least a as titanium content control element in electron donor compound and the catalyzer reagent and at least a titanium compound after make.
Above-mentioned anhydrous magnesium compound is magnesium dihalide, alkyl halide magnesium or alkoxyl group magnesium halide, preferably oxyethyl group magnesium halide such as oxyethyl group magnesium chloride, normal-butyl magnesium halide such as oxyethyl group magnesium chloride or anhydrous magnesium dichloride, and titanium compound is mainly TiCl
4, TiBr
4, Ti (OR)
4In one or more mixture; Alkylol cpd is C
1～C
8Monohydroxy-alcohol or dibasic alcohol, a kind of in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, the 2-ethyl hexanol or more than one mixture are preferably arranged; The reagent that is used as titanium content control element in electron donor and the catalyzer is Ti (OR)
4, R is C in the formula
1～C
10Alkyl, preferred Ti (OC
4H
9)
4
The material that is used as activator component is that general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, n is 1～3 number.The preferred triethyl aluminum of activator, triisobutyl aluminium or aluminium diethyl monochloride, the preferred chlorine or bromine of X.
The above-mentioned catalyzer that contains titanium component can adopt following method preparation:
(1) handle adding alkylol cpd in the anhydrous magnesium compound under the nitrogen protection, the mol ratio of anhydrous magnesium compound and alkylol cpd is 1: 1～1: 20, after heated and stirred refluxed 2～4 hours, and cooling-sedimentation, filtering supernatant liquid.
(2) the inorganic magnesium compound with above-mentioned processing joins in the dispersion reagent, adds activator component, heated and stirred 0.5-4 hour, adds Ti (OR) down at 40～120 ℃
4, R is the alkyl of C1～C10 in the formula, the compound of C4～C6 preferably, the Ti of adding (OR)
4Can be 1 with the mol ratio of anhydrous magnesium compound: (5-40), being generally 1: 40, is 1: 10 preferably, and best is 1: 5.Reacted 0.5-6 hour.Cooling, filtration are stayed and are done back usefulness.
(3) in step 2 gained grey black solid, add TiCl
4Or TiCl
4With Ti (OR)
4Mixture 90～130 ℃ of reactions 0.5～3 hour, the solid of gained through the anhydrous inert solvent washing, after the vacuum-drying, is promptly obtained loaded catalyst.
Dispersion agent in the above-mentioned steps 2 includes but not limited to: the alkane of heptane, octane, nonane, decane, C11---C20 and their mixture thereof.
Anhydrous inert solvent in the above-mentioned steps 3 includes but not limited to: the alkane of hexane, heptane, octane, C9---C12 and their mixture thereof.
Catalyst system provided by the invention has following significant advantage:
1. come the charge capacity of titanium in the control catalyst by the add-on of titanate compound, thereby realized control catalyst efficient, stable polymerization reaction, easy control of temperature has been avoided the caking and the wall sticking phenomenon of polymkeric substance in the polymerization process.
2. compare with the technology of existing preparation polyethylene catalysts,, improved the energy for growth of polymkeric substance on the catalyst activity position, reduced the ash content in the polymkeric substance by strengthening modification to the active centre.
3. be raw material with the anhydrous magnesium compound, especially with oxyethyl group magnesium chloride or normal-butyl chlorination magnesium be that the catalyst particles granularity that makes of raw material is moderate, narrow diameter distribution, good fluidity, the tap density of resulting polymers is bigger, helps the mass transfer in the polymerization process and the conveying of material.
4. by reflow treatment, improved the particle form of catalyzer, thereby can obtain the polymkeric substance that granularity is good, be evenly distributed the anhydrous magnesium compound.
5. compare with the existing catalyzer that has used on the polyethylene production device, this catalyst preparation technology operating procedure is simple, the three wastes are few, and excellent industrial application foreground is arranged.
The catalyzer that the present invention relates to can be used in that ethylene homo closes or the copolymerization of ethene and other alkene, is applicable to vapor phase process, slurry process and solution method polymerization technique.The catalyst charge mode that both had been suitable for dry powder form also is suitable for the catalyst charge mode of slurry form.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
1. melting index: press ASTMD1238-99 and measure;
2. density: press ASTMD-1505 and measure;
3. active: with the quality representation of every gram catalyzer gained resin;
Embodiment 1
1. Preparation of Catalyst
In the there-necked flask of the 250ml that blows row through nitrogen, add 3g oxyethyl group magnesium chloride, according to the mol ratio of anhydrous magnesium compound and alkylol cpd is that 1: 15 ratio adds ethanol, reflux stirred 2 hours, cool to room temperature, filter the back toward wherein adding the 30ml heptane, according to anhydrous magnesium compound and organo-aluminium compound mol ratio is that 2: 1 ratio adds triethyl aluminum, slowly is warmed up to 60 ℃ and adds 2mlTi (OC
4H
9)
4, isothermal reaction 2 hours, cooling, filtering behind the supernatant liquid according to anhydrous magnesium compound and halogenated titanium mol ratio is 1: 20 ratio adding TiCl
4, being heated to 120 ℃ of reactions 2 hours, cool to room temperature is used hexane wash 5 times, and vacuum-drying gets the canescence catalyzer, and Ti content is 3.84wt% in this catalyzer, and Mg content is the slurry catalyst that 7.86wt%. is configured to 1mg/ml, stays and does down usefulness.
2. polymerization experiment
The 10L polymerization reaction kettle is vacuumized inflated with nitrogen more earlier, and this operates triplicate, adds the 3000ml hexane, add 200ml polymerization-grade hexene-1,0.01mol 25 milligrams of triethyl aluminum and above-mentioned solid catalysts add hydrogen 0.1MPa, feed ethene, control reactor pressure is at 1.0MPa, and polymerization temperature is controlled at 80 ℃～85 ℃, polymerization 2.5 hours, get polymkeric substance 985g, experimental result is seen attached list.
Embodiment 2
1. Preparation of Catalyst
In the there-necked flask of the 250ml that blows row through nitrogen, add 3g normal-butyl chlorination magnesium, according to the mol ratio of anhydrous magnesium compound and oxygenatedchemicals is that 1: 20 ratio adds ethanol, reflux stirred 2 hours, cool to room temperature, filter the back toward wherein adding the 30ml heptane, according to anhydrous magnesium compound and organo-aluminium compound mol ratio is that 2: 1 ratio adds triisobutyl aluminium, slowly is warmed up to 60 ℃ and adds 2mlTi (OC
4H
9)
4, isothermal reaction 2 hours, cooling, filter behind the supernatant liquid according to the anhydrous magnesium compound with the halogenated titanium mol ratio be that 1: 20 ratio adds TiCl
4, being heated to 120 ℃ of reactions 2 hours, cool to room temperature is used hexane wash 5 times, and vacuum-drying gets the canescence catalyzer, and Ti content is 3.46wt% in this catalyzer, and Mg content is the slurry catalyst that 7.38wt%. is configured to 1mg/ml, stays and does down usefulness.
2. polymerization experiment
Polymerization process is with embodiment 1, and polymerization 2.5 hours gets polymkeric substance 847g, and experimental result is seen attached list.
Embodiment 3
1. Preparation of Catalyst
In the there-necked flask of the 250ml that blows row through nitrogen, add 3g oxyethyl group magnesium chloride, according to the mol ratio of anhydrous magnesium compound and oxygenatedchemicals is that 1: 15 ratio adds butanols, reflux stirred 2 hours, cool to room temperature, filter the back toward wherein adding the 30ml heptane, according to anhydrous magnesium compound and organo-aluminium compound mol ratio is that 2: 1 ratio adds triethyl aluminum, slowly is warmed up to 60 ℃ and adds 2mlTi (OC
4H
9)
4, isothermal reaction 2 hours, cooling, filter behind the supernatant liquid according to the anhydrous magnesium compound with the halogenated titanium mol ratio be that 1: 20 ratio adds Ti (OC
4H
9)
4With TiCl
4Mixture (Ti (OC
4H
9)
4: TiCl
4=1: 5) be heated to 120 ℃ of reactions 2 hours, cool to room temperature is used hexane wash 5 times, and vacuum-drying gets the canescence catalyzer, and Ti content is 2.75wt% in this catalyzer, and Mg content is the slurry catalyst that 8.42wt%. is configured to 1mg/ml, stays and does down usefulness.
2. polymerization experiment
Polymerization process is the same, gets polymkeric substance 723g, and experimental result is seen attached list.
Embodiment 4
1. Preparation of Catalyst
In the there-necked flask of the 250ml that blows row through nitrogen, add the anhydrous magnesium dichloride of 3g, according to the mol ratio of anhydrous magnesium compound and oxygenatedchemicals is that 1: 15 ratio adds butanols, reflux stirred 2 hours, cool to room temperature, filter the back toward wherein adding the 30ml heptane, according to anhydrous magnesium compound and organo-aluminium compound mol ratio is that 1: 2 ratio adds aluminium diethyl monochloride, slowly is warmed up to 60 ℃ and adds 2mlTi (OC
10H
21)
4, isothermal reaction 2 hours, cooling, filter behind the supernatant liquid according to the anhydrous magnesium compound with the halogenated titanium mol ratio be that 1: 20 ratio adds Ti (OC
10H
21)
4With TiCl
4Mixture (Ti (OC
10H
21)
4: TiCl
4=1: 5) be heated to 120 ℃ of reactions 2 hours, cool to room temperature is used hexane wash 5 times, and vacuum-drying gets the canescence catalyzer, and Ti content is 2.75wt% in this catalyzer, and Mg content is the slurry catalyst that 8.42wt%. is configured to 1mg/ml, stays and does down usefulness.
2. polymerization experiment
Polymerization process is the same, gets polymkeric substance 470g, and experimental result is seen attached list.
Embodiment 5
1. Preparation of Catalyst
Except that the mol ratio of anhydrous magnesium compound and oxygenatedchemicals is 1: 1, other is with embodiment 1, and in the gained catalyzer, Ti content is 1.94wt%, and Mg content is 9.26wt%.
2 polymerization experiment
Polymerization process gets polymkeric substance 320g with embodiment 1, and experimental result is seen attached list.
Embodiment 6
1. Preparation of Catalyst
Except that the oxygenatedchemicals spent glycol, other is with embodiment 1, and in the gained catalyzer, Ti content is 5.82wt%, and Mg content is 5.16wt%.
2. polymerization experiment
Polymerization process gets polymkeric substance 380g with embodiment 1, and experimental result is seen attached list.
Embodiment 7
1. Preparation of Catalyst
Removing the titanic acid ester that adds is Ti (OCH
3)
4Outward, other is with embodiment 1, and in the gained catalyzer, Ti content is 3.26wt%, and Mg content is 7.22wt%.
2. polymerization experiment
Polymerization process gets polymkeric substance 880g with embodiment 1, and experimental result is seen attached list.
Embodiment 8
1. Preparation of Catalyst
Remove the Ti (OC that adds
4H
9)
4Outside 0.25ml, other is with embodiment 1, and in the gained catalyzer, Ti content is 6.26wt%, and Mg content is 8.22wt%.
2. polymerization experiment
Polymerization process gets polymkeric substance 480g with embodiment 1, and experimental result is seen attached list.
Subordinate list: polymerization experiment result
| Catalyzer | Polymerization activity (KgPE/gcat.) | MI (g/10min) | Density (g/ml) |
| Embodiment 1 | 39.4 | 0.81 | 0.924 |
| Embodiment 2 | 33.9 | 1.26 | 0.920 |
| Embodiment 3 | 28.9 | 1.63 | 0.928 |
| Embodiment 4 | 18.8 | 0.92 | 0.918 |
| Embodiment 5 | 12.7 | 1.51 | 0.921 |
| Embodiment 6 | 15.0 | 2.09 | 0.925 |
| Embodiment 7 | 34.8 | 1.08 | 0.923 |
| Embodiment 8 | 19.1 | 2.65 | 0.927 |
Claims (5)
1. one kind is used for ethylene polymerization catalysts, its main ingredient is: handling with alkylol cpd on the carrier of anhydrous magnesium compound gained, add at least a activator component, at least a as titanium content control element in electron donor compound and the catalyzer reagent and at least a titanium compound after make, described anhydrous magnesium compound is alkoxyl group magnesium halide or alkyl halide magnesium, and described alkylol cpd is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol or the propylene glycol or more than one mixture; The described reagent that is used as titanium content control element in electron donor and the catalyzer is Ti (OR)
4, R is C in the formula
1～C
10Alkyl; Described titanium compound is TiCl
4Or TiCl
4With Ti (OR)
4Mixture, R is C in the formula
1～C
10Alkyl; The described material that is used as activator component is selected from triethyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride, and described catalyzer adopts the preparation method who comprises the following steps to make:
(a) handle adding alkylol cpd in alkoxyl group magnesium halide or the alkyl halide magnesium under the nitrogen protection, the mol ratio of alkoxyl group magnesium halide or alkyl halide magnesium and alkylol cpd is 1: 1～1: 20, after heated and stirred refluxed 2～4 hours, cooling-sedimentation, filtering supernatant liquid;
(b) alkoxyl group magnesium halide or the alkyl halide magnesium with above-mentioned processing joins in the dispersion reagent, adds activator component, heated and stirred 0.5-4 hour, adds Ti (OR) down at 40～120 ℃
4, R is C in the formula
1～C
10Alkyl, reacted 0.5-6 hour, cooling, filter, stay and do the back and use;
(c) in step (b) gained grey black solid, add TiCl
4Or TiCl
4With Ti (OR)
4Mixture 90～130 ℃ of reactions 0.5～3 hour, the solid of gained through the anhydrous inert solvent washing, after the vacuum-drying, is promptly obtained loaded catalyst.
2. be used for ethylene polymerization catalysts according to claim 1, it is characterized in that, described alkoxyl group magnesium halide is the oxyethyl group magnesium halide; Described alkyl halide magnesium is the normal-butyl magnesium halide.
3. be used for the preparation method of ethylene polymerization catalysts according to claim 1, comprise the following steps:
(a) handle adding alkylol cpd in the anhydrous magnesium compound under the nitrogen protection, the mol ratio of alkoxyl group magnesium halide or alkyl halide magnesium and alkylol cpd is 1: 1～1: 20, after heated and stirred refluxed 2～4 hours, cooling-sedimentation, filtering supernatant liquid, described anhydrous magnesium compound are alkoxyl group magnesium halide or alkyl halide magnesium;
(b) alkoxyl group magnesium halide or the alkyl halide magnesium with above-mentioned processing joins in the dispersion reagent, adds activator component, heated and stirred 0.5-4 hour, adds Ti (OR) down at 40～120 ℃
4, R is C in the formula
1～C
10Alkyl, reacted 0.5-6 hour, cooling, filter, stay and do the back and use;
(c) in step (b) gained grey black solid, add TiCl
4Or TiCl
4With Ti (OR)
4Mixture 90～130 ℃ of reactions 0.5～3 hour, the solid of gained through the anhydrous inert solvent washing, after the vacuum-drying, is promptly obtained loaded catalyst.
4. as being used for the preparation method of ethylene polymerization catalysts as described in the claim 3, it is characterized in that the dispersion agent in the described step (b) is selected from heptane, octane, nonane, decane or C
11-C
20Alkane in one or more.
5. as being used for the preparation method of ethylene polymerization catalysts as described in the claim 3, it is characterized in that the anhydrous inert solvent in the described step (c) is selected from hexane, heptane, octane or C
9-C
12Alkane in one or more.
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|---|---|---|---|
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|---|---|---|---|
| CN2009100484742A CN101519464B (en) | 2009-03-27 | 2009-03-27 | Catalyst for vinyl polymerization or copolymerization as well as preparation and application thereof |
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| CN101519464B true CN101519464B (en) | 2011-05-11 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532211A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
| CN1552743A (en) * | 2003-05-29 | 2004-12-08 | 中国石油化工股份有限公司 | Catalyst for ethene polymerization or multipolymer, preparing method thereof |
| CN1814627A (en) * | 2005-02-02 | 2006-08-09 | 北京金鼎科化工科技有限公司 | Catalyst active constituent and catalyst containing same |
| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
-
2009
- 2009-03-27 CN CN2009100484742A patent/CN101519464B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532211A (en) * | 2003-03-18 | 2004-09-29 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
| CN1552743A (en) * | 2003-05-29 | 2004-12-08 | 中国石油化工股份有限公司 | Catalyst for ethene polymerization or multipolymer, preparing method thereof |
| CN1814627A (en) * | 2005-02-02 | 2006-08-09 | 北京金鼎科化工科技有限公司 | Catalyst active constituent and catalyst containing same |
| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
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