CN106632759A - Solid catalyst component for ethylene polymerization, preparation method and application thereof - Google Patents
Solid catalyst component for ethylene polymerization, preparation method and application thereof Download PDFInfo
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- CN106632759A CN106632759A CN201510718809.2A CN201510718809A CN106632759A CN 106632759 A CN106632759 A CN 106632759A CN 201510718809 A CN201510718809 A CN 201510718809A CN 106632759 A CN106632759 A CN 106632759A
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- solid catalyst
- ingredient
- catalyst
- inorganic oxide
- magnesium
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Abstract
The invention relates to a solid catalyst component for ethylene polymerization. An inorganic oxide is taken as a carrier and a reaction product of magnesium halide, titanium halide and a silicate compound is loaded. The invention also relates to a preparation method of the solid catalyst component and a catalyst for ethylene polymerization reaction. The solid catalyst component disclosed by the invention is high in polymerization activity when used for ethylene polymerization reaction, and the melt index and the hydrogen regulation sensitivity are high.
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, Z-N catalyst is widely used.
In published patent, most magnesium halides are carrier, using different methods so that catalyst has very high
Activity and preferable particle condition, but general hydrogen regulation performance is not ideal.
In disclosed patent ZL02146016, there is provided a kind of ethylene rolymerization catalyst, by catalyst system
A kind of silicon compound containing alkyl is added during standby so that catalyst has high activity and excellent hydrogen tune sensitivity
Property.
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 melt index and hydrogen response are high.
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 product of magnesium halide, halogenated titanium and phosphate compound is loaded.
According to the present invention, the phosphate compound, with activated centre effect, is improved and urged as electron donor
Agent hydrogen regulation performance.
A specific embodiment of the invention, the phosphate compound is selected from salicylic acid diethylphosphate
Ester, triethyl phosphate and tributyl phosphate.
A specific embodiment of the invention, the magnesium halide is selected from magnesium dichloride, dibrominated magnesium and diiodo-
Change magnesium, preferred magnesium dichloride.
A specific embodiment of the invention, the halogenated titanium is selected from titanium chloride and titanium bromide, preferred trichlorine
Change titanium and/or titanium tetrachloride.
According to one embodiment of present invention, the magnesium halide is calculated as with the mol ratio of the halogenated titanium with Mg/Ti
1：(0.1-10).The halogenated titanium is calculated as 1 with the phosphate compound with Ti/P：(0.05-5) it is, excellent
Elect 1 as：(0.1-2), more preferably 1：(0.4-1.5).
According to the present invention, described inorganic oxide carrier can select the oxide of silicon and/or aluminium, its oxide grain
Footpath is 0.01-10 μm, and preferable particle size is 0.01-2 μm, more preferably 0.1-2 μm.Most preferably inorganic oxide is
0.1-1 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, the hybrid reaction of magnesium halide, halogenated titanium and phosphate compound is obtained
To mother liquor, afterwards mother liquor and inorganic oxide carrier blending are obtained into slurry liquid, finally slurry liquid is sprayed
It is dried to obtain 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 5-30wt%.
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, and 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 120-190 DEG C, the outlet temperature of spray drying device is 60-130 DEG C, preferably
90-105℃。
A specific embodiment of the invention, the organic solvent is selected from C1-C4Aliphatic saturated monocarboxylic acid
Arrcostab, C7-C8The Arrcostab of aromatic carboxylic acids, C2-C6Aliphatic ether, C3-C4Cyclic ethers and C3-C6Saturated fat
Ketone, is preferably selected from methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydrofuran, acetone
And methyl iso-butyl ketone (MIBK), most preferably tetrahydrofuran.
A specific embodiment of the invention, 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；Can also 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 described organo-aluminium
Ratio between compound and the ingredient of solid catalyst is with Al/Ti molar ratio computings as (20-500)：1, preferably
(50-200)：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 is selected from propylene, butylene, amylene, hexene, octene and 4- methylpentenes -1.Its polymerization
Technique adopts vapor phase method, slurry process or solwution method, more suitable for gas fluidised bed polymerisation.
The present invention, as carrier, loads the anti-of magnesium halide, halogenated titanium and phosphate compound using inorganic oxide
Answer product as ingredient of solid catalyst, high performance solid catalysis are prepared by spray drying forming mode
Agent, its catalysis activity is high, and hydrogen response and high melt index.
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) melt index is determined using ASTM D1238-99.
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, 2.6g salicylic acids diethylphosphate and 100ml tetrahydrofurans, 65 DEG C are warming up under stirring, here
At a temperature of isothermal reaction 3 hours.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-610,0.02-0.1 μm), the mother liquor after cooling is added, 35 DEG C of keeping temperature, after stirring 1 hour,
Mother liquor after silica gel is blended is spray-dried with spray dryer, spray condition：190 DEG C of inlet temperature,
105 DEG C of outlet temperature, obtains solid catalyst, and wherein Ti content is 2.3wt%.
(2) ethene slurry polymerization
1L hexanes will be added in the 2L polymeric kettles that row is blown through nitrogen, while adding the triethyl aluminum of 1mmol
With 0.02g solid catalysts, 75 DEG C of addition hydrogen 0.18Mpa are warming up to, hydrogenation adds ethene after finishing
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 3.9g that difference is the amount of salicylic acid diethylphosphate, and spray condition is：
190 DEG C of inlet temperature, 100 DEG C of outlet temperature, polymerization result is shown in Table 1.
Embodiment 3
With embodiment 1, it is 5.2g that difference is the amount of salicylic acid diethylphosphate, and spray condition is：
190 DEG C of inlet temperature, 101 DEG C of outlet temperature, 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 65 DEG C are warming up under 100ml tetrahydrofurans, stirring, isothermal reaction 3 hours at this temperature.It is cooled to
35℃。
Addition 6g silica gel (Cabot Corporation in the 250ml there-necked flasks of row are blown to one through nitrogen
TS-610,0.02-0.1 μm), the mother liquor after cooling is added, 35 DEG C of keeping temperature, after stirring 1 hour,
Mother liquor after silica gel is blended is spray-dried with spray dryer, spray condition：195 DEG C of inlet temperature,
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 solid for loading the product of magnesium halide, halogenated titanium and phosphate compound is urged
When agent component is used as major catalyst, polymerization activity is higher, and high melt index.It is polymerized under similarity condition
The melt index of product is higher, represents that its hydrogen regulation performance is better.Accordingly, it is shown that solid of the invention is urged
When agent component is used as major catalyst, its hydrogen response is high.
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 and phosphate compound.
2. ingredient of solid catalyst according to claim 1, it is characterised in that the phosphate compound
Selected from salicylic acid diethylphosphate, triethyl phosphate and tributyl phosphate.
3. according to the ingredient of solid catalyst described in claim 1 or 2, it is characterised in that the magnesium halide
1 is calculated as with the mol ratio of the halogenated titanium with Mg/Ti：(0.1-10)；And/or the halogenated titanium and the phosphoric acid
The mol ratio of ester compounds is calculated as 1 with Ti/P：(0.05-5), preferably 1：(0.1-2), more preferably 1：
(0.4-1.5)。
4. the ingredient of solid catalyst according to any one in claim 1-3, it is characterised in that described
The particle diameter of inorganic oxide is 0.01-10 μm, preferably 0.01-2 μm, more preferably 0.1-1 μm；And/or institute
Inorganic oxide is stated for silica and/or aluminum oxide.
5. a kind of method for preparing ingredient of solid catalyst described in any one in claim 1-4, including：
In organic solvent, magnesium halide, halogenated titanium and phosphate compound hybrid reaction are obtained into mother liquor, afterwards by mother liquor
Blending is carried out with inorganic oxide and obtain slurry liquid, finally spray drying is carried out to slurry liquid and obtain solid catalysis
Agent.
6. method according to claim 5, it is characterised in that the temperature of the reaction is 65-95 DEG C,
The pressure of the reaction is 0.8-2MPa, and the time of the reaction is 0.5-3 hours；And/or
The temperature during blending is 10-70 DEG C；And/or
The condition of the spray drying is：The inlet temperature of spray drying device is 80-240 DEG C, preferably
120-190 DEG C, the outlet temperature of spray drying device is 60-130 DEG C, preferred 90-105 DEG C.
7. method according to claim 5, it is characterised in that the magnesium halide selected from magnesium dichloride, two
Magnesium bromide and magnesium diiodide；And/or the halogenated titanium is selected from titanium chloride and titanium bromide；And/or the organic solvent
Selected from C1-C4The Arrcostab of aliphatic saturated monocarboxylic acid, C7-C8The Arrcostab of aromatic carboxylic acids, C2-C6Aliphatic ether, C3-C4
Cyclic ethers and C3-C6Saturated fat ketone, be preferably selected from methyl formate, ethyl acetate, butyl acetate, ether, oneself
Ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK).
8. a kind of catalyst for vinyl polymerization, including the product of following component：
A. it is any one in the ingredient of solid catalyst or claim 5-7 in claim 1-4 described in any one
Ingredient of solid catalyst prepared by item methods described；
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.
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 (20-500)：1, preferably (50-200)：1.
10. appoint in the ingredient of solid catalyst or claim 5-7 according to any one in claim 1-4
Catalyst described in the ingredient of solid catalyst or claim 8 or 9 of one methods described preparation of meaning is poly- in ethene
Application in conjunction.
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|---|---|---|---|---|
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
| CN101775086A (en) * | 2009-01-09 | 2010-07-14 | 中国石油天然气股份有限公司 | Preparation method for ethylene homopolymer and copolymer |
| CN101838352A (en) * | 2009-03-20 | 2010-09-22 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof |
| CN102585057A (en) * | 2011-01-05 | 2012-07-18 | 中国石油化工股份有限公司 | Catalyst for vinyl polymerization reaction |
-
2015
- 2015-10-29 CN CN201510718809.2A patent/CN106632759B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
| CN101775086A (en) * | 2009-01-09 | 2010-07-14 | 中国石油天然气股份有限公司 | Preparation method for ethylene homopolymer and copolymer |
| CN101838352A (en) * | 2009-03-20 | 2010-09-22 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof |
| CN102585057A (en) * | 2011-01-05 | 2012-07-18 | 中国石油化工股份有限公司 | Catalyst for vinyl polymerization reaction |
Non-Patent Citations (1)
| Title |
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| 王月娜: "《聚丙烯酯类内给电子体化合物的合成与催化性能研究》", 《硕士毕业论文-中国石油大学（北京）》 * |
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