CN106632756A - Solid catalyst component for vinyl polymerization as well as preparation and application of solid catalyst component - Google Patents
Solid catalyst component for vinyl polymerization as well as preparation and application of solid catalyst component Download PDFInfo
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- CN106632756A CN106632756A CN201510717546.3A CN201510717546A CN106632756A CN 106632756 A CN106632756 A CN 106632756A CN 201510717546 A CN201510717546 A CN 201510717546A CN 106632756 A CN106632756 A CN 106632756A
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- solid catalyst
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- halohydrin
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Abstract
The invention relates to a solid catalyst component for a vinyl polymerization reaction. The preparation method comprises the following steps: the solid catalyst component comprises inorganic oxides as carriers, and reaction products from magnesium halide, titanium halide, halohydrin and silane compounds, which are loaded on inorganic oxides. The invention further relates to a preparation method of the solid catalyst component, and a catalyst used for the vinyl polymerization reaction. The solid catalyst component disclosed by the invention is high in polymerization activity when being used for the vinyl polymerization reaction, and the obtained polymer is high in bulk density and low in oligomer content.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of catalyst and its preparation for ethylene polymerization
Method.
Background technology
In the polymerisation or ethene of ethene and the copolymerization of alpha-olefin, the performance impact of catalyst poly-
The performance of compound.Some oligomer can be produced while catalyst vinyl polymerization, oligomer makes sub-polyethylene
Force-bearing situation between son changes, and affects the performance and processing characteristics of product, and its surrender to product is strong
Degree, elongation and rigidity etc. all have an impact.The number of oligomer is general to be weighed with the number of hexane extract,
Therefore, hexane extract number be also weigh catalyst performance an important indicator.
Ucat-J catalyst adopts slurries dosing form, meets condensation mode, but needs another on process units
Outer outfit slurry charging system, increased the popularization difficulty of such catalyst.Therefore existing catalyst is changed
Enter, exploitation is applicable for use with condensation operation pattern, and can be used for without slurry catalyst charging system
The high activity solid catalyst of UNIPOL technique polyethylene production devices is very necessary and significant.
The content of the invention
For deficiency of the prior art, the invention provides it is a kind of with inorganic oxide as carrier for ethene
The supported solid catalyst component of polymerisation.The catalyst prepared using the ingredient of solid catalyst is used as master
Catalyst carries out ethylene polymerization, and catalysis activity is high, and oligomer is low in resulting polymers.
According to an aspect of the invention, there is provided a kind of ingredient of solid catalyst for ethylene polymerization,
Including：With inorganic oxide as carrier, the reaction of magnesium halide, halogenated titanium, halohydrin and silane compound is loaded
Product.
According to the present invention, the formula of the silane compound is R4R3Si(OR1)(OR2), wherein R1、R2、R3
And R4It is identical or different, it is each independently C1-C20Straight or branched alkyl or C3-C20Cycloalkyl；
Preferably C1-C6Straight or branched alkyl or C3-C6Cycloalkyl.
A specific embodiment of the invention, the silane compound is selected from methylcyclohexyl dimethoxy silicon
Alkane.
According to the present invention, the halohydrin formula is XnROH, wherein R are selected from C1-C10Straight or branched
Alkyl, C3-C10Cycloalkyl and C6-C20Monocyclic or polycyclic aromatic group, and the alkyl, cycloalkanes
N hydrogen atom in base or aromatic group is replaced by X, and X is selected from halogen, is preferably selected from fluorine, chlorine and bromine,
N is the integer of 1≤n≤3.
According to a particular embodiment of the invention, the halohydrin include 2,2,2- ethapons, 2,2- dichlroroethanols,
The chloro- 1- hexanols of ethylene chlorhydrin, 3- chloropropyl alcohols, 6-, the bromo- 1- propyl alcohol of 3-, the chloro- 1- amylalcohols of 5-, the chloro- n-butyl alcohols of 4-, 6-
At least one in amino -1- hexanols and 2- chloro cyclohexanols.
A specific embodiment of the invention, the magnesium halide is selected from magnesium dichloride, dibrominated magnesium and diiodo-
Change magnesium.
Another specific embodiment of the invention, the halogenated titanium is selected from titanium trichloride and/or titanium tetrachloride.
According to another embodiment of the invention, the halogenated titanium and the mol ratio of the halohydrin are 1：
(0.5-20), preferably 1：(1-10).The mol ratio of the magnesium halide and the halogenated titanium in terms of Mg/Ti,
For 1：(0.1-10).The halogenated titanium is 1 with the mol ratio of the Cyclohexylmethyldimethoxysilane：
(1-600), preferably 1：(20-200).
According to the present invention, described inorganic oxide carrier can select the oxide of silicon and/or aluminium, and its particle diameter is usual
For 0.01-10 μm, preferable particle size 0.01-5 μm, more preferably 0.01-2 μm.Most preferably inorganic oxide is
0.01-1 μm of silica supports.The catalyst particle shape that silica gel under this particle diameter is generated is good, and intensity is high, is difficult
It is broken.
According to another aspect of the present invention, there is provided a kind of system of the ingredient of solid catalyst for vinyl polymerization
Preparation Method, including：In organic solvent, it is the mixing of magnesium halide, halogenated titanium, halohydrin and silane compound is anti-
Mother liquor should be obtained, afterwards mother liquor and inorganic oxide carrier blending slurry liquid is obtained into, finally slurry liquid is carried out
Spray drying obtains described ingredient of solid catalyst.
A specific embodiment of the invention, the inorganic oxide carrier should be when in use drying
, i.e., the water not adsorbed.Sufficient amount of carrier and mother liquor should be mixed, formation is suitable for being sprayed
The slurry liquid that mist is dried.With the slurry liquid gross weight meter, the inorganic oxide carrier is 5-50wt%, excellent
Select 10-30wt%.
According to method of the present invention, the temperature of the reaction is 65-95 DEG C, and the pressure of the reaction is
0.8-2MPa, the time of the reaction is 0.5-3 hours.The temperature of the blending is 10-70 DEG C.
According to method of the present invention, the condition of the spray drying is：The inlet temperature of spray drying device
For 80-240 DEG C, preferred 120-180 DEG C, the outlet temperature of spray drying device is 60-130 DEG C, preferred 90-110
℃。
With the gross weight meter of the slurry liquid, the amount of the inorganic oxide is 5-50wt%, preferred 10-30wt%.
A specific embodiment of the invention, the organic solvent is conventional organic solvent in the art.
The organic solvent is selected from tetrahydrofuran, and in terms of every mole of Ti, the amount of the organic solvent is 1-600 mole,
Preferably 20-200 mole.
According to another aspect of the present invention, there is provided a kind of catalyst for vinyl polymerization, including such as the following group
The product divided：
A. the above-mentioned ingredient of solid catalyst for ethylene polymerization；
B. organo-aluminum compound, the organo-aluminum compound formula is AlR 'nX3-n, R ' is hydrogen or C in formula1-C20
Alkyl, X is halogen, and n is the integer of 1≤n≤3.
According to the present invention, in order that the ingredient of solid catalyst obtained after being spray-dried is applied to production vinyl polymerization
Thing, it is necessary to be employed as the organo-aluminum compound of activator and reduce the titanium atom in the ingredient of solid catalyst
Into the state that can make ethene effectively polymerization.Usually, in varsol, by the solid catalytic ingredient with
Activator is reacted, and obtains the catalyst, it is also possible in the course of the polymerization process by the ingredient of solid catalyst
Reacted with activator component, so as to cause olefinic polyreaction.Described varsol selected from isopentane,
Hexane, heptane, toluene, dimethylbenzene, naphtha and mineral oil.
A specific embodiment of the invention, the organo-aluminum compound includes triethyl aluminum, triisobutyl
At least one in aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium or aluminium diethyl monochloride.Wherein as activator group
Part the organo-aluminum compound in aluminium and the ingredient of solid catalyst in the mol ratio of titanium be (5-500)：
1, preferably (10-200)：1.
According to the present invention, described catalyst is applied to the copolymerization of the homopolymerization of ethene or ethene and other alpha-olefins
Close, alpha-olefin therein may be selected from propylene, butylene, amylene, hexene, octene and 4- methylpentenes -1
Kind.Its polymerization technique adopts vapor phase method, slurry process and solwution method, more suitable for gas fluidised bed polymerisation.
The present invention is using inorganic oxide as carrier, load magnesium halide, halogenated titanium, halohydrin and silane chemical combination
The product of thing has obtained highly active catalyst as ingredient of solid catalyst by spray shaping mode,
Resulting polymers bulk density is high, and the oligomer in prepared polymer is low.
Specific embodiment
Technical scheme is described further with reference to embodiment, but is not constituted to the present invention's
Any restriction.
Analysis and characterization in the present invention is as follows：
(1) bulk density：Using (ASTM D1895) plastics apparent density, bulkfactor and pouring into property
Test method be measured；
(2) fine powder content：Sieved using standard screen.
The synthesis of used catalyst composition is carried out in a nitrogen atmosphere.
Embodiment 1
(1) preparation of catalyst
The TiCl that 1.5g is successively added in the 250ml there-necked flasks of row is blown through nitrogen to one4, 4.4g it is anhydrous
MgCl2, 6.1g ethapons, the 1mmol/ml of 100ml tetrahydrofurans (100% analysis pure) and 10ml
65 DEG C are warming up under Cyclohexylmethyldimethoxysilane, stirring, at this temperature isothermal reaction 3 hours.Drop
Temperature is to 35 DEG C.
Addition 6g silica gel (Cabot Corporation in the 250ml there-necked flasks of row are blown to one through nitrogen
TS-610, particle diameter is 0.02-0.1 μm), the mother liquor after cooling is added, 35 DEG C of keeping temperature, stirring 1 is little
Shi Hou, the mother liquor after silica gel is blended is spray-dried with spray dryer, spray condition：Inlet temperature 180
DEG C, 110 DEG C of outlet temperature obtains solid catalyst, and wherein Ti content is 2.2wt%.
(2) ethene slurry polymerization
1L hexanes will be added in the 2L polymeric kettles that row is blown through nitrogen, while add the 1mmol/ml of 1ml
Triethyl aluminum and 0.03g solid catalysts, are warming up to 75 DEG C of addition hydrogen 0.18Mpa, and hydrogenation is added after finishing
Ethene 0.75Mpa, is warmed up to 85 DEG C, and after reacting 2 hours, cooling discharge, polymerization result is shown in Table 1.
Embodiment 2
With embodiment 1, it is 12.2g that difference is the amount of ethapon, and the titanium in gained solid catalyst contains
Measure as 2.2wt%, polymerization result is shown in Table 1.
Embodiment 3
With embodiment 1, it is 15.3g that difference is the amount of ethapon, and the titanium in gained solid catalyst contains
Measure as 2.3wt%, polymerization result is shown in Table 1.
Comparative example 1
(1) preparation of catalyst
Blow in the 250ml there-necked flasks of row through nitrogen to one and successively add 1.5gTiCl4, the anhydrous MgCl of 4.0g2
With 100ml tetrahydrofurans (100% analysis is pure), 65 DEG C are warming up under stirring, at this temperature isothermal reaction 3
Hour.It is cooled to 35 DEG C.
Addition 6g silica gel (Cabot Corporation in the 250ml there-necked flasks of row are blown to one through nitrogen
TS-610, particle diameter is 0.02-0.1 μm), the mother liquor after cooling is added, 35 DEG C of keeping temperature, stirring 1 is little
Shi Hou, the mother liquor after silica gel is blended is spray-dried with spray dryer, spray condition：Inlet temperature 195
DEG C, 110 DEG C of outlet temperature obtains ingredient of solid catalyst, and wherein Ti content is 2.4wt%.
(2) ethene slurry polymerization is with embodiment 1.Polymerization result is shown in Table 1.
Table 1
Can be seen that under same polymerizing condition from the aggregated data of table 1, compared to comparative example 1, adopt
With inorganic oxide as carrier, the product of magnesium halide, halogenated titanium, halohydrin and silane compound is loaded
When ingredient of solid catalyst is used as major catalyst, polymerization activity is higher, and the bulk density of resulting polymers is high,
Oligomer low (numerical value of ＜ 75 μm (wt%) is little).The particle diameter of described polymer beads is at 75-850 μm
In the range of content it is high, be conducive to the commercial Application of polymer.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of ingredient of solid catalyst for ethylene polymerization, including：With inorganic oxide as carrier,
The product of load magnesium halide, halogenated titanium, halohydrin and silane compound.
2. ingredient of solid catalyst according to claim 1, it is characterised in that the silane compound
Formula is R4R3Si(OR1)(OR2), wherein R1、R2、R3And R4It is identical or different, it is each independently C1-C20
Straight or branched alkyl or C3-C20Cycloalkyl；Preferably C1-C6Straight or branched alkyl or
C3-C6Cycloalkyl.
3. ingredient of solid catalyst according to claim 1 and 2, it is characterised in that the halohydrin leads to
Formula is XnROH, wherein R are selected from C1-C10Straight or branched alkyl, C3-C10Cycloalkyl and C6-C20
Monocyclic or polycyclic aromatic group, and n hydrogen atom in the alkyl, cycloalkyl or aromatic group is by X
Replaced, X is halogen, be preferably selected from fluorine, chlorine, bromine and iodine, n is the integer of 1-3；
It is preferred that the halohydrin include 2,2,2- ethapons, 2,2- dichlroroethanols, ethylene chlorhydrin, trimethylene chlorohydrin,
The chloro- 1- hexanols of 6-, the bromo- 1- propyl alcohol of 3-, the chloro- 1- amylalcohols of 5-, the chloro- n-butyl alcohols of 4-, 6- amino -1- hexanols and 2- chlorine hexamethylenes
At least one in alcohol.
4. the ingredient of solid catalyst according to any one in claim 1-3, it is characterised in that described
Halogenated titanium is 1 with the mol ratio of the halohydrin：(0.5-20), preferably 1：(1-10)；The magnesium halide and institute
The mol ratio of halogenated titanium is stated in terms of Mg/Ti, is 1：(0.1-10)；The halogenated titanium and the silane compound
Mol ratio is calculated as 1 with Ti/Si：(1-600), preferably 1：(20-200).
5. the ingredient of solid catalyst according to any one in claim 1-4, it is characterised in that described
The particle diameter of inorganic oxide is 0.01-10 μm, preferably 0.01-5 μm, more preferably 0.01-1 μm；And/or institute
Inorganic oxide is stated for silica and/or aluminum oxide.
6. a kind of method for preparing ingredient of solid catalyst described in any one in claim 1-5：Including：
In organic solvent, magnesium halide, halogenated titanium, halohydrin and silane compound hybrid reaction are obtained into mother liquor, afterwards
Mother liquor and inorganic oxide are carried out into blending and obtains slurry liquid, finally spray drying is carried out to slurry liquid and obtain solid
Catalytic component.
7. method according to claim 6, it is characterised in that the condition of the spray drying is：Spraying
The inlet temperature of drying equipment is 80-240 DEG C, and preferred 120-180 DEG C, the outlet temperature of spray drying device is
60-130 DEG C, preferred 90-110 DEG C；And/or the organic solvent is selected from tetrahydrofuran.
8. a kind of catalyst for vinyl polymerization, including the product of following component：
A. it is square described in the ingredient of solid catalyst or claim 6 or 7 in claim 1-5 described in any one
Ingredient of solid catalyst prepared by method；
B. organo-aluminum compound, the formula of the organo-aluminum compound is AlR 'nX3-n, in formula R ' be hydrogen or
C1-C20Alkyl, X is halogen, and n is the integer of 1≤n≤3.
9. catalyst according to claim 8, it is characterised in that between component B and component A
Ratio with Al/Ti molar ratio computings as (5-500):1, preferably (10-200):1.
10. the ingredient of solid catalyst or claim 6 or 7 according to any one in claim 1-5
Catalyst described in the ingredient of solid catalyst or claim 8 or 9 of methods described preparation is in vinyl polymerization
Using.
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| CN201510717546.3A CN106632756B (en) | 2015-10-29 | 2015-10-29 | Ethylene polymerization ingredient of solid catalyst and its preparation and application |
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| CN201510717546.3A CN106632756B (en) | 2015-10-29 | 2015-10-29 | Ethylene polymerization ingredient of solid catalyst and its preparation and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625334A (en) * | 1991-10-09 | 1994-02-01 | Tonen Corp | Catalyst for polymerizing alpha-olefin |
| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
| CN101024708A (en) * | 2007-02-05 | 2007-08-29 | 中国科学院长春应用化学研究所 | Method for preparing broad-peak polythenel montmorillonite nano composite material using mixed catalyst |
| CN101289520A (en) * | 2008-06-07 | 2008-10-22 | 淄博新塑化工有限公司 | Catalyst suitable for vinyl polymerization and copolymerisation |
-
2015
- 2015-10-29 CN CN201510717546.3A patent/CN106632756B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625334A (en) * | 1991-10-09 | 1994-02-01 | Tonen Corp | Catalyst for polymerizing alpha-olefin |
| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
| CN101024708A (en) * | 2007-02-05 | 2007-08-29 | 中国科学院长春应用化学研究所 | Method for preparing broad-peak polythenel montmorillonite nano composite material using mixed catalyst |
| CN101289520A (en) * | 2008-06-07 | 2008-10-22 | 淄博新塑化工有限公司 | Catalyst suitable for vinyl polymerization and copolymerisation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
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