CN102585056A - Catalyst for vinyl polymerization or copolymerization reaction - Google Patents
Catalyst for vinyl polymerization or copolymerization reaction Download PDFInfo
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- CN102585056A CN102585056A CN2011100009110A CN201110000911A CN102585056A CN 102585056 A CN102585056 A CN 102585056A CN 2011100009110 A CN2011100009110 A CN 2011100009110A CN 201110000911 A CN201110000911 A CN 201110000911A CN 102585056 A CN102585056 A CN 102585056A
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- catalyzer
- vinyl polymerization
- copolymerization
- electron donor
- polymerization
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Abstract
The invention relates to a catalyst for vinyl polymerization or copolymerization reaction, a method for producing the same and an application thereof. The catalyst comprises the reaction products of the following components: (1) titaniferous active component: magnesium dihalide, at least one titanium halide, at least one electron donor compound and a nitriles compound which has a formula of RCN are loaded on a superfine inorganic oxide carrier, wherein R is alkyl which has 1-10 carbon atoms, and the electron donor compound is selected from ether, ester or ketone; and (2) activating agent component: organo-alumnium compound which has the formula of AlR'nX3-n, wherein in the formula, R' is alkyl which has 1-20 carbon atoms, X is halogen, and n is not larger than 3 but is larger than 1. The catalyst has higher catalyst activity and better catalyst hydrogen regulation performance when being used for vinyl homo-polymerization or the copolymerization of vinyl and other alpha-olefin.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, and this Preparation of catalysts method and purposes.
Technical background
In the copolymerization of the polyreaction of ethene or ethene and terminal olefin, Ziegler-Natta catalyst is widely used.In disclosed patent, most is carrier with the magnesium halide, adopts diverse ways, on carrier, make catalyzer that very high activity and particle condition preferably arranged, but generally hydrogen regulation performance is not ideal the active constituent loading of transition metal.In CN03816816, in system, add alcohol compound to MgCl
2Dissolving improve, but the catalyst activity of this system is not high, the hydrogen regulation performance of catalyzer is satisfactory inadequately.The inventor finds through TE, in described catalyst system, introduces a certain proportion of nitrile compounds, can improve the hydrogen regulation performance of activity of such catalysts and catalyzer.
Summary of the invention
The present invention provides a kind of catalyzer that is used for vinyl polymerization or copolymerization; It adopts tetrahydrofuran solvent that magnesium dihalide is dissolved; And add a certain proportion of nitrile compounds; Mix back loading on silica-gel carrier with transition metal component, thereby improved the hydrogen regulation performance of activity of such catalysts and catalyzer.
The present invention provides a kind of catalyzer that is used for vinyl polymerization or copolymerization, and it comprises the reaction product of following component:
(1) titaniferous active ingredient: a kind of magnesium dihalide, at least a halogenated titanium, at least a electron donor compound and general formula are arranged is the nitrile compounds of RCN in load on the ultra-fine inorganic oxide carrier; Wherein R is that carbonatoms is 1～10 alkyl, and described electron donor compound is selected from ether, ester or ketone;
(2) activator component: general formula is AlR '
nX
3-nOrgano-aluminium compound, R ' is 1～20 alkyl for hydrogen or carbonatoms in the formula, X is a halogen, 1＜n≤3.
Wherein, described electron donor compound is selected from ether, ester or ketone, concrete as: C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8Aromatic carboxylic acid alkyl ester, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers, C
3～C
6A kind of in the saturated fatty ketone or their mixture, preferable formic acid methyl esters, ETHYLE ACETATE, butylacetate, ether, hexyl ether, THF, acetone and MIBK etc., most preferably THF.These electron donors can use separately, also can mix use.
Described halogenated titanium is titanium chloride or titanium bromide, preferred TiCl
3Or TiCl
4
Described general formula is the nitrile compounds of RCN, and wherein R is that carbonatoms is 1～10 alkyl, and preferred R is that carbonatoms is 1～4 alkyl.For example: methyl, ethyl, propyl group or butyl etc.Concrete compound is like formonitrile HCN, acetonitrile, propionitrile, butyronitrile, preferred acetonitrile.
The mol ratio of said halogenated titanium and nitrile compounds is 1: 0.05～20, preferred 1: 0.1～10; The ratio of said halogenated titanium and magnesium dihalide is: 0.1＜magnesium/titanium＜10; It is 1 mole to 600 moles that the add-on of electron donor generally is controlled at every mole of titanium, is preferably 20 moles to 200 moles.
Described ultra-fine inorganic oxide carrier is generally selected the oxide compound of silicon and/or aluminium for use, and its particle diameter is generally 0.01～10 micron, and preferable particle size is more selected 0.1～2 micron, most preferably 0.1～1 micron silica supports less than 5 microns.
Above-mentioned titaniferous active ingredient can adopt following method preparation:
(1) mother liquor preparation:
In the electron donor compound, be that the nitrile compounds of RCN carries out the prepared in reaction mother liquor in said ratio with magnesium compound, halogenated titanium and general formula;
(2) carrier blending:
The mother liquor of preparation in the step (1) and ultra-fine inorganic oxide carrier are carried out blending obtain slurry; Wherein carrier should be exsiccant in use, does not promptly have the water of absorption.Should the carrier of sufficient amount be mixed with mother liquor mutually, formation is suitable for carrying out spray-dired slurry, and promptly the content of this carrier is 5～50 weight % in slurry, preferred 5～30 weight %.
(3) spray shaping:
The slurry that obtains in the step (2) is carried out spraying drying, obtain ingredient of solid catalyst.Spray condition: inlet temperature 80-240 ℃, temperature out 60-130 ℃.
In order to make the ingredient of solid catalyst that obtains after the spraying drying be applicable to the production ethene polymers, must adopt organo-aluminium compound that the titanium atom in the said catalyst component is reduced into and to make the effective polymeric state of ethene.Usually, in varsol, ingredient of solid catalyst and activator component that step (3) obtains are reacted, obtain catalyzer; The ingredient of solid catalyst and the activator component that also can in polymerization process, step (3) be obtained are reacted, thereby cause olefinic polyreaction.
Described activator component is general formula AlR '
nX
3-nOrgano-aluminium compound; R ' is 1～20 alkyl for hydrogen or carbonatoms in the formula; X is a halogen, and n is the number of 1＜n≤3, concrete as: a kind of in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium or the aluminium diethyl monochloride or their mixture.Wherein in the acvator component in aluminium and the titaniferous active ingredient mol ratio of titanium be 5～500, preferred 10～200.
Described varsol such as iso-pentane, hexane, heptane, toluene, YLENE, petroleum naphtha and mineral wet goods.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other terminal olefins, and terminal olefin is wherein selected a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1 for use.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation.
The present invention provides a kind of catalyzer that is used for vinyl polymerization or copolymerization, and it adopts tetrahydrofuran solvent that magnesium chloride is dissolved, and adds a certain proportion of nitrile compounds, thereby has improved the hydrogen regulation performance of activity of such catalysts and catalyzer.
Embodiment
Testing method:
1, activity: the weight with every gram catalyzer gained resin is represented
2, melting index: ASTM-D 1238
Embodiment given below is for the present invention is described, rather than limits the invention.
Embodiment 1
(1) Preparation of catalysts
Blow through nitrogen to one and successively to add 1.5 gram TiCl in row's the 250ml there-necked flask
4, 4.0 the gram anhydrous MgCl
2, 0.68 gram acetonitrile and 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot Corporation TS-610, particle diameter are the 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added; Keep 35 ℃ of temperature, stir after 1 hour, with the mother liquor after the silica gel blending with spray-dryer (instrument model: BUCHI Mini Spray Dryer B-191) carry out spraying drying; 195 ℃ of the inlet temperatures of spray-dryer; 110 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein titanium content is 2.2wt%.
(2) ethene slurry polymerization
To pass through and add 1 liter of hexane in 2 liters of polymeric kettles that nitrogen blows row, add triethyl aluminum and the 0.03 gram catalyzer of 1 milliliter of 1mmol simultaneously, and be warming up to 75 ℃ and add hydrogen 0.18Mpa; After finishing, hydrogenation adds ethene 0.75Mpa; Be warmed up to 85 ℃, react after 2 hours cooling discharge.Polymerization result is seen table 1.
Embodiment 2
(1) Preparation of catalysts is with embodiment 1.Just the amount of acetonitrile is 1.0 grams, and the titanium content of gained ingredient of solid catalyst is 2.3Wt%.
(2) the ethene slurry polymerization is with embodiment 1.Polymerization result is seen table 1.
Embodiment 3
(1) Preparation of catalysts is with embodiment 1.Just the amount of acetonitrile is 0.5 gram, and the titanium content of gained ingredient of solid catalyst is 2.3wt%.
(2) the ethene slurry polymerization is with embodiment 1.Polymerization result is seen table 1.
Comparative Examples 1
(1) Preparation of catalysts
Blow through nitrogen to one and successively to add 1.5 gram TiCl in row's the 250ml there-necked flask
4, 4.0 the gram anhydrous MgCl
2With the 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot Corporation TS-610, particle diameter are the 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added; Keep 35 ℃ of temperature, stir after 1 hour, the mother liquor after the silica gel blending is carried out spraying drying with spray-dryer; 195 ℃ of the inlet temperatures of spray-dryer; 110 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein titanium content is 2.4wt%.
(2) the ethene slurry polymerization is with embodiment 1.Polymerization result is seen table 1.
Can find out that from the aggregated data of table 1 under same polymerizing condition, catalyst activity of the present invention is higher, and has higher melting index, demonstrates hydrogen regulation performance preferably.
Table 1
Claims (13)
1. catalyzer that is used for vinyl polymerization or copolymerization comprises the reaction product of following component:
(1) titaniferous active ingredient: a kind of magnesium dihalide, at least a halogenated titanium, at least a electron donor compound and general formula are arranged is the nitrile compounds of RCN in load on the ultra-fine inorganic oxide carrier; Wherein R is that carbonatoms is 1～10 alkyl, and described electron donor compound is selected from ether, ester or ketone;
(2) activator component: general formula is AlR '
nX
3-nOrgano-aluminium compound, R ' is 1～20 alkyl for hydrogen or carbonatoms in the formula, X is a halogen, 1＜n≤3.
2. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that said ultra-fine inorganic oxide carrier is a particle diameter less than 5 microns silicon-dioxide.
3. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that said ultra-fine inorganic oxide carrier is that particle diameter is 0.1～1 micron a silicon-dioxide.
4. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described halogenated titanium is selected from titanous chloride or titanium tetrachloride.
5. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described electron donor compound is selected from C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8Aromatic carboxylic acid alkyl ester, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers, C
3～C
6A kind of in the saturated fatty ketone or their mixture.
6. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described electron donor compound is selected from methyl-formiate, ETHYLE ACETATE, butylacetate, ether, hexyl ether, THF, acetone and MIBK.
7. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described electron donor compound is selected from THF.
8. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described magnesium dihalide is magnesium dichloride, dibrominated magnesium or two magnesium iodides.
9. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described activator component is selected from a kind of in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium or the aluminium diethyl monochloride or their mixture.
10. the catalyzer that is used for ethylene polymerization according to claim 1 is characterized in that described general formula is in the nitrile compounds of RCN, and R is that carbonatoms is 1～4 alkyl.
11. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described nitrile compounds is an acetonitrile.
12. the described Preparation of catalysts method that is used for vinyl polymerization or copolymerization of one of claim 1-11, it may further comprise the steps:
(1) mother liquor preparation: in the electron donor compound, be that the nitrile compounds of RCN carries out the prepared in reaction mother liquor with magnesium dihalide, halogenated titanium and general formula;
(2) carrier blending: the mother liquor of step (1) preparation and ultra-fine inorganic oxide carrier are carried out blending obtain slurry;
(3) slurry that obtains in the step (2) is carried out spraying drying, obtain ingredient of solid catalyst;
(4) prereduction: in MO, ingredient of solid catalyst and described activator component that step (3) obtains are reacted, obtain catalyzer.
13. the described application that is used for the catalyzer of vinyl polymerization or copolymerization at vinyl polymerization or copolymerization of one of claim 1-11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100009110A CN102585056A (en) | 2011-01-05 | 2011-01-05 | Catalyst for vinyl polymerization or copolymerization reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100009110A CN102585056A (en) | 2011-01-05 | 2011-01-05 | Catalyst for vinyl polymerization or copolymerization reaction |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250315A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN104250322A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst component for ethene polymerization and catalyst |
| CN109438595A (en) * | 2018-09-29 | 2019-03-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of ethene gas-phase polymerization slurry type catalyst and preparation method thereof |
| CN112812205A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction, catalyst thereof, preparation method and application thereof |
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| US4376062A (en) * | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
| CN1726230A (en) * | 2002-12-18 | 2006-01-25 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN1993384A (en) * | 2004-07-28 | 2007-07-04 | 三井化学株式会社 | Olefin polymerization catalyst and method of polymerization using the catalyst |
| CN101842396A (en) * | 2007-11-01 | 2010-09-22 | 三井化学株式会社 | Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method |
-
2011
- 2011-01-05 CN CN2011100009110A patent/CN102585056A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4376062A (en) * | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
| CN1726230A (en) * | 2002-12-18 | 2006-01-25 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN1993384A (en) * | 2004-07-28 | 2007-07-04 | 三井化学株式会社 | Olefin polymerization catalyst and method of polymerization using the catalyst |
| CN101842396A (en) * | 2007-11-01 | 2010-09-22 | 三井化学株式会社 | Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250315A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN104250322A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst component for ethene polymerization and catalyst |
| CN104250322B (en) * | 2013-06-28 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for ethylene polymerization |
| CN109438595A (en) * | 2018-09-29 | 2019-03-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of ethene gas-phase polymerization slurry type catalyst and preparation method thereof |
| CN109438595B (en) * | 2018-09-29 | 2021-05-04 | 吉化集团吉林市天龙催化剂有限公司 | Ethylene gas phase polymerization slurry type catalyst and preparation method thereof |
| CN112812205A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction, catalyst thereof, preparation method and application thereof |
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Application publication date: 20120718 |