CN109369830A - Solid activating agent system and preparation method thereof - Google Patents
Solid activating agent system and preparation method thereof Download PDFInfo
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- CN109369830A CN109369830A CN201811114081.2A CN201811114081A CN109369830A CN 109369830 A CN109369830 A CN 109369830A CN 201811114081 A CN201811114081 A CN 201811114081A CN 109369830 A CN109369830 A CN 109369830A
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Abstract
The present invention relates to a kind of solid activating agent systems, it is made of a kind of reaction product of trimethyl aluminium (TMA) and acid in the presence of carrier, it is reacted by a kind of acid with trimethyl aluminium (TMA) and prepares a kind of solid activating agent, activator prepared by this method has very high activity and longer shelf-life, and easy to operate.The activator of the method preparation has adsorbed on a solid carrier, therefore the step of eliminating MAO activator-support.Furthermore water is replaced to be easier to control reaction process by acid, thus the activator of method preparation has competitiveness very much on production cost.
Description
Technical field
The present invention relates to a kind of solid activating agent, in particular to a kind of olefin polymerization solid activating agent and its preparation
Method.
Background technique
Methylaluminoxane (MAO) is one of most important industrial aikyiaiurnirsoxan beta.MAO can with metal complex, such as metallocene shape
At olefinic polymerization single site catalysts (SSC), used as activator (or co-catalyst).These catalyst be used to give birth to
Polyolefin is produced, application includes but is not limited to polyethylene (PE) and polypropylene (PP).
MAO can be prepared by trimethyl aluminium (TMA) partial hydrolysis:
This reaction is strong exothermal reaction, and process is difficult to control, and a variety of methods have been used for controlling its production process, for example,
Small-scale continuous reaction process can be used for direct hydrolysis.
The product is the dynamic mixing of Multiple components, and is not completely understood.The product is extremely hazardous, need
Want stringent security system, including anhydrous and oxygen-free environment.
In addition, activity is often limited, it is therefore desirable to excessive MAO, to ensure the activity of industrial application, this meeting
Increase cost.The shelf life of products is very limited, generally requires cryopreservation.
Finally, polymerization may cause reactor dirt with the catalyst that MAO is activated.MAO and metal complex generally require
Appendix is in solid material, such as silica gel.This may further decrease its activity.
Therefore, there is still a need for a better activators for olefin polymerization catalysis.
Summary of the invention
It is an object of the invention to overcome the shortcomings of above-mentioned prior art, a kind of preparation process is provided and is easier to control, is urged
It is more preferable to change activity, the holding time is more long, is capable of the solid activating agent system of substituent methyl aikyiaiurnirsoxan beta, reacts shape with metallocene
At manufacture of polyolefins catalyst.
It realizes the technical scheme is that a kind of solid activating agent system, is being carried by trimethyl aluminium (TMA) and a kind of acid
Reaction product composition in the presence of body.
A kind of preparation method of solid activating agent system is reacted in the presence of carrier by trimethyl aluminium with acid.
The preparation method of above-mentioned solid activating agent system, carrier are inorganic oxide or organic material.
The preparation method of above-mentioned solid activating agent system is silica, aluminium oxide, aluminium when carrier is inorganic oxide
It is a kind of in silicate or clay.
The preparation method of above-mentioned solid activating agent system is carbon black when carrier is organic material, polyolefin, and polyolefin is total
Polymers, porous styrene polymer are a kind of in porous styrol copolymer.
The preparation method of above-mentioned solid activating agent system, acid are that alkyl of the carbon number range from C1 to C50 replaces acid or poly-
Acid.The preparation method of above-mentioned solid activating agent system, acid include formic acid, and acetic acid, propionic acid, butyric acid, 2 ethyl hexanoic acid, oneself two
Acid, citric acid, malonic acid, succinic acid, maleic acid, fumaric acid, benzoic acid are a kind of in benzene binary acid.
The preparation method of above-mentioned solid activating agent system, acid include in boric acid, alkylboronic acids and R2BOH and its derivative
It is a kind of.
The preparation method of above-mentioned solid activating agent system, acid are benzoic acid, and carrier is silica gel.
The preparation method of above-mentioned solid activating agent system, acid are boric acid, and carrier is silica gel.
Above-mentioned solid activating agent system, the Al/O molar ratio range of solid activating agent are 0.1:1 to 10:1.
The preparation method of upper solid activating agent system, before trimethyl aluminium is added, acid is first reacted with carrier.
The preparation method of above-mentioned solid activating agent system, before addition of the acid, trimethyl aluminium are first reacted with carrier.
The preparation method of above-mentioned solid activating agent system, before carrier is added, acid is first reacted with trimethyl aluminic acid.
The preparation method of above-mentioned solid activating agent system, reaction are carried out at 0 DEG C to 200 DEG C.
The preparation method of above-mentioned solid activating agent system, reaction carry out in atent solvent.
The Al/O molar ratio of the preparation method of above-mentioned solid activating agent system, trimethyl aluminium and acid is 0.1:1 to 1:
0.1。
A kind of olefin polymerization catalysis, by the anti-of solid activating agent system in the above method and transition metal complex compound
Answer product.
A kind of application of olefin polymerization catalysis uses above-mentioned catalyst in olefin polymerization.
Composition of the invention is included in the presence of a kind of carrier, and trimethyl aluminium is reacted with acid.
In one embodiment of the invention, the preparation of invention activator should use the hydrocarbon solvent of non-aromatic class.
In another embodiment of the present invention, the preparation of invention activator, in the presence of silica.
In another embodiment of the present invention, the activator preparation of invention, first by boric acid and silicon dioxde reaction, then
It is reacted with TMA.
In another embodiment of the present invention, the preparation of the activator of invention, in the presence of silica benzoic acid
It is reacted with TMA.
In another embodiment of the present invention, activator Yu transient metal complex (metallocene or the single activity of invention
Center catalyst) form active olefin polymerization catalysis.
In another embodiment of the present invention, in the activator of invention and (or) the polyene prepared from the activator of invention
Implement olefin polymerization in the presence of hydrocarbon catalyst.
Acid
Single, double substituted carboxylic acid and polycarboxylic acids may be selected in acid.Since term used herein " alkyl group " or " alkyl " are one
As use in meaning, this is well known application.Specifically, it refers to that one group has a carbon atom to be directly connected to
The rest part of one molecule, and there are a kind of main hydrocarbyl characteristics.
Monocarboxylic acid may include the formula of acid:
R-COOH
Wherein R is hydrogen, or is replaced, non-substituted alkyl, naphthenic base, alkenyl, cycloalkenyl group or aryl group include from 1 to
50 carbon atoms.The example of this acid includes formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitinic acid, stearic acid, cyclohexane-carboxylic acid,
2- methyl carboxylic acids, 4- methyl carboxylic acids, oleic acid, linoleic acid, linolenic acid acid, hexamethylene -2-eneoic- acid, benzoic acid, 2- methylbenzene first
Acid, 3- methyl benzoic acid, 4- methyl benzoic acid, salicylic acid, 2- hydroxy-4-methyl benzoic acid, 2- hydroxyl -4- acetyl salicylic acid,
P- P-hydroxybenzoic acid, 3,5- di-tert-butyl-4-hydroxybenzoic acids, ortho-aminobenzoic acid, p-aminobenzoic acid, O-methoxy benzene
Formic acid and P- methoxy benzoic acid.
Dicarboxylic acids may include the formula of acid:
HOOC-(CH2)n-COOH
Wherein n is zero or integer, including such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid are pungent
Diacid.Further include the acid of following formula:
Wherein x is zero or integer, and y is zero or integer, and x and y may be identical or different, and R is hydrogen, or replace, is non-substituted
Alkyl, naphthenic base, alkenyl, cycloalkenyl group, aryl (include the carbon from 1 to 50).The example of this acid includes alkyl or alkenyl amber
Acid, 2- dimethyl succinic acid, 2 ethyl glutaric acid, 2-N- dodecyl succinic acid, 2-N- dodecenyl succinic succinic acid, 2- phenyl fourth
Diacid, 2- (P- aminomethyl phenyl) succinic acid.It further include polysubstituted alkyl dicarboxylic aid, wherein other R groups on substitutable alkyl group chain.
Such as: 2,2- dimethyl succinic acids 2,3- dimethyl succinic acid, 2,3,4- trimethyl, 2,3,4- trimethyl glutaric acid, 2,2,3- tri-
Methyl-glutaric acid；2- ethyl -3- dimethyl succinic acid.
Binary acid further includes the formula of acid:
HOOC-(CrH2r-2)COOH
Wherein r is an integer, the number of two or more.Such as maleic acid, fumaric acid, 2- glutaconate, 2- hexene diacid,
3- hexene diacid, 5- methyl -2- enedioic acid, -2 glutaconate of 2,3- dimethyl；2- methyl-2-butene diacid；2- dodecane
Base-butene dioic acid；2- polyethylene isobutene-(E)-butenedioic acid.
Binary acid further includes aromatic dicarboxylic acid, such as phthalic acid, and M-phthalic acid, terephthalic acid (TPA) and substitution are adjacent
Phthalic acid, formula are as follows:
Wherein R refers to above-mentioned group, n=1,2,3 or 4, work as n > 1, then R may be identical or different group.
The example of this acid includes: 3- methylbenzene -1,2- dicarboxylic acids；4- biphenyl -1,3- dicarboxylic acids；2- (1- acrylic) benzene -1,4- two
Carboxylic acid；3,4- dimethylbenzene -1,2- dicarboxylic acids.
Acid is also possible to the form of boric acid or hydroxide and its salt, such as B (OH)3、RB(OH)2And R2BOH and its derivative
Object.
Carrier
The carrier of any organic or inorganic can be used.Useful carrier is larger with typically being characterized in having in invention
Surface area porous and granular or particulate solid form organic or inorganic compound.Inorganic material preferentially selects, for example, dioxy
SiClx, aluminium oxide-silicon oxide mix glue, aluminium oxide, zirconium oxide, magnesia, magnesium chloride, float stone, talcum, clay and its mixture.
Or combined with inorganic material, organic material particles include, for example, polystyrene, polyethylene, polypropylene gather
Carbonic ester, carbon black, etc..
Suitable inorganic compound, including inorganic oxide, hydroxide or salt；Porous oxide is first choice, including example
Such as silica, aluminium oxide, magnesia, zirconium oxide, titanium dioxide, boron oxide, zinc oxide, barium monoxide and its mixture, including
Such as silica-magnesia, silica-alumina, silica-titania.Non-oxidized substance particle, example can also be used
Such as magnesium chloride.Preferred carrier include silica, alchlor be main component.Or mixtures thereof inorganic oxide can be into one
Step includes a small amount of carbonate, sulfate, nitrate and oxide, etc..
One carrier usually have the following characteristics that average diameter of particles about at 10 microns to 300 microns, it is preferably micro- 20
Rice is between 200 microns, and for example, about 30 microns to 100 microns；At least about 80 angstroms of pore size, it is therefore desirable to reach about 100
Angstrom；Pore volume about 0.3 cubic centimetre/gram to 2.5 cubic centimetres/gram.In another example of the invention, more than preparation
Before described specific catalyst, and its carrier can be first in 100 DEG C of -700 DEG C of temperature calcinations.
Preferred carrier includes silica.The size of the particle of preferred SiO2 will depend on whether to be used for gas phase
Catalyst in polymerization process, or slurry polymerization process or solution polymerization process.Typical SiO2With porosity about 0.2 to about
2.5 mls/g, preferably 0.3 to about 2.0 ml/g, most preferably about 0.5 to about 1.5 ml/g, pore volume can make
With BET technology, and probe molecule is used nitrogen as to test.
Carried catalyst preparation
The preparation of carried catalyst can be reacted in the presence of solid carrier by acid and TMA to be made.Acid can first be reacted with TMA,
Then increase solid carrier.Or acid or TMA are first mixed with carrier, are then reacted respectively with TMA or acid.
In an example of the present invention, reaction can carry out in inert hydrocarbon solvent.For example, benzene, toluene and petroleum
Ether.Reaction temperature can control within about 0-200 DEG C temperature range.Al/O molar ratio is controlled in 0.1/1-1/0.1 range
Between.Product after reaction can be washed further with atent solvent and selectively be dried.
For example, controlling the range from 0.3/1 to 1/0.3 of O/Al in inert environments, temperature is heated to 200 DEG C by 40 DEG C,
Benzoic acid and TMA are in SiO2With reacted in the presence of petroleum ether about 0.5-24 hours.Resulting mixture is cleaned with heptane,
Obtain carried catalyst.
In another example boric acid can be with silicon dioxde reaction under the conditions of refluxing toluene.Resulting mixture can be anti-with TMA
It should obtain carried catalyst.
Transition metal complex compound (single site catalysts or metallocene compound) and the above-mentioned load reacted
The reaction of body activator can prepare olefin polymerization catalysis, this method is more common.Generally from periodic table of elements 3-10 group, such as
Iron, cobalt, nickel, zinc, vanadium, manganese etc. select suitable single active center by Metallocenyl or the compound for replacing Metallocenyl to form
Or metallocene compound.Such as the 4th group of transition metal in the periodic table of elements, such as Ti, Zr, Hf, Rf.These compounds include
Titanocenes-zirconium dichloride (bimetallocenyl zirconium dichloride) and ethylidene-indenyl-zirconium dichloride, but
Have a considerable amount of compounds by called optical imaging.
Solid activating agent or catalyst of the invention can be adapted for any olefin polymetiation process generally carried out.For example,
Gas phase process, suspension technology, solution process.There may be the removings of additional moisture and air in olefin polymerization process
Agent.Example includes alkyl aluminum, alkyl magnesium, Mixed bittern substituting metal.
Composition of the invention is as metal complex, as metallocene forms olefinic polymerization single site catalysts
(SSC) it during, is used as activator or co-catalyst.These catalyst be used to produce polyolefin, and application includes
But it is not limited to polyethylene (PE) and polypropylene (PP).PE and PP comes plastics with the most use at last, total value in 2010 according to volume
Reach 120,000,000 tonne, accounts for 63% (Chemical market federation, CMA) in whole world high molecular polymer.Agricultural is with thin
Film, non-woven fabrics fiber, industrial container and milk tank are several examples of its purposes.
For the number and specification of quantity represented in present specification and claims, percentage or ratio
It is outer except as otherwise indicating with other numerical value used in claims, it is understood to numerical value " about ", in all situations
Under all allow modify.
It therefore, can be according to not unless indicating on the contrary, the parameter in following description and claims is interpreted as approximate
With demand characteristics and be varied.Rather than attempt the application range of limitation claim, the parameter of each numerical value at least may be used
To pass through the method interpretation that rounds up generally used according to number of significant digit.
Although it have been described that specific example, but substitute, it modifies, variation, improves and some unpredictalbe at present
The thing being substantially equal, it is possible that other applicants.Therefore, the purpose that can be modified in appended claims is
It may include these substitutions, modify, change, improvement and substantially the same thing.
Beneficial effects of the present invention: (1) there is activator prepared by this method very high activity to guarantee the quality with longer
Phase, and it is easy to operate；(2) activator of the method preparation on a solid carrier, therefore eliminates MAO activator-support
The step of, furthermore replace water to be easier to control reaction process by acid；(3) thus the activator of method preparation is non-on production cost
Often with competitive.
Specific embodiment
(embodiment 1)
The present embodiment uses the following raw material: trimethyl aluminium；Carrier: silica；Acid: formic acid.
Weigh trimethyl aluminium 0.72kg (10mol)；Silica 50kg；Formic acid 4.6kg (100mol), spare, inertia is molten
Agent toluene 250kg, wherein the molar ratio of trimethyl aluminium and formic acid is 0.1:1.
It is fitted into atent solvent toluene 250kg in reaction vessel, is heated to 100 DEG C, stir 10 minutes, trimethyl is added
Then aluminium 0.72kg is slowly added to carrier silicas 50kg while stirring, is kept stirring, after reaction carries out 2 hours, slowly add
Entering formic acid 4.6kg, reaction temperature is maintained at 100 DEG C or so, and it reacts 4 hours, filters out solid, cleaned again, centrifugal dehydration,
Obtain product solid activator system.
Above-mentioned product 11.6kg (200mol Al) is weighed, and metallocene ferrocene 0.186kg (1mol), after hybrid reaction
Generate olefin polymerization catalysis.The olefin polymerization catalysis is applied in manufacture of polyolefins.
(embodiment 2)
The present embodiment uses the following raw material: trimethyl aluminium；Carrier: silica gel；Acid: boric acid, wherein trimethyl aluminium and boric acid
Molar ratio is 1:0.1.
Weigh trimethyl aluminium 7.2kg；Silica gel 500kg；Boric acid 0.61kg, spare, atent solvent toluene 2500kg.
It is fitted into atent solvent toluene 2500kg in reaction vessel, is heated to 100 DEG C, stir 10 minutes, trimethyl is added
Then aluminium 7.2kg is slowly added to carrier boric acid 0.61kg while stirring, is kept stirring, after reaction carries out 2 hours, be slowly added to
Silica gel 500kg, reaction temperature are maintained at 100 DEG C or so, react 4 hours, filter out solid, cleaned again, centrifugal dehydration, obtained
To product solid activator system.
Above-mentioned product 11.6kg (200mol Al) kg is weighed, with metallocene ferrocene 0.186kg (1mol) kg, mixing is anti-
Should after generate olefin polymerization catalysis.The olefin polymerization catalysis is applied in manufacture of polyolefins.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (21)
1. a kind of preparation method of solid activating agent system, it is characterised in that: deposited by trimethyl aluminium (TMA) and a kind of acid in carrier
It is reacted to obtain the solid activating agent system under；Wherein, the acid is that alkyl of the carbon number range from C1 to C50 replaces carboxylic
Acid, polycarboxylic acids, boric acid or alkylboronic acids, the carrier are that have the porous and granular of large surface area or having for particulate solid form
The Al/O molar ratio range of machine or inorganic compound, the trimethyl aluminium and acid is 1:0.3 to 10:1；Also, due to being to carry
It is prepared in the presence of body, the activator on a solid carrier, to save the carrier step of preparation process, and reacted
Journey is relatively easy to control, easy to operate, lower production costs, while prepared solid activating agent activity with higher and more
The long shelf-life.
2. preparation method according to claim 1, wherein the carrier be have large surface area porous and granular or
The organic or inorganic compound of grain solid form, wherein the carrier is inorganic oxide, organic material or carbon black.
3. preparation method according to claim 2, wherein being silica, oxidation when the carrier is inorganic oxide
Aluminium, aluminosilicate or clay.
4. preparation method according to claim 2, wherein being polyolefin or porous benzene when the carrier is organic material
Ethene polymers.
5. the preparation method according to claim 4, wherein the porous styrene polymer is that porous styrene is total
Polymers.
6. preparation method according to claim 1, wherein the acid is formic acid, acetic acid, propionic acid, butyric acid, 2 ethyl hexanoic acid,
Adipic acid, citric acid, malonic acid, succinic acid, maleic acid, fumaric acid, benzoic acid or benzene binary acid.
7. preparation method according to claim 1, wherein the acid is benzoic acid, the carrier is silica gel.
8. preparation method according to claim 1, wherein the acid is boric acid, the carrier is silica gel.
9. preparation method according to claim 1, wherein acid is first reacted with carrier before trimethyl aluminium is added.
10. preparation method according to claim 1, wherein before addition of the acid, trimethyl aluminium is first reacted with carrier.
11. preparation method according to claim 1, wherein acid is first reacted with trimethyl aluminium before carrier is added.
12. preparation method according to claim 1 carries out at a temperature of 0 DEG C to 200 DEG C wherein reacting.
13. preparation method according to claim 1 carries out in atent solvent wherein reacting.
14. preparation method according to claim 1 comprising:
Weigh trimethyl aluminium 0.72kg i.e. 10mol；Silica 50kg；Formic acid 4.6kg, that is, 100mol, spare, atent solvent first
Benzene 250kg, wherein the molar ratio of trimethyl aluminium and formic acid is 0.1:1；
It is fitted into atent solvent toluene 250kg in reaction vessel, is heated to 100 DEG C, stir 10 minutes, trimethyl aluminium is added
Then 0.72kg is slowly added to carrier silicas 50kg while stirring, is kept stirring, after reaction carries out 2 hours, be slowly added to
Formic acid 4.6kg, reaction temperature are maintained at 100 DEG C or so, react 4 hours, filter out solid, cleaned again, centrifugal dehydration, obtained
To product solid activator system.
15. preparation method according to claim 1 comprising:
Weigh trimethyl aluminium 7.2kg；Silica gel 500kg；Boric acid 0.61kg, spare, atent solvent toluene 2500kg, wherein trimethyl
The molar ratio of aluminium and boric acid is 1:0.1；
It is fitted into atent solvent toluene 2500kg in reaction vessel, is heated to 100 DEG C, stir 10 minutes, trimethyl aluminium is added
Then 7.2kg is slowly added to carrier boric acid 0.61kg while stirring, is kept stirring, after reaction carries out 2 hours, be slowly added to silicon
Glue 500kg, reaction temperature are maintained at 100 DEG C or so, react 4 hours, filter out solid, cleaned again, centrifugal dehydration, obtained
Product solid activator system.
16. a kind of olefin polymerization catalysis, to be activated by the solid of any one of claim 1 to the 15 preparation method preparation
The reaction product of agent system and transition metal complex compound.
17. catalyst according to claim 16, wherein the transition metal complex compound is metallocene compound.
18. catalyst according to claim 17, wherein the metallocene compound is metallocene ferrocene.
19. a kind of preparation method of olefin polymerization catalysis described in claim 16 comprising:
Solid activating agent system is prepared, step is as claimed in claim 14；
The i.e. 200mol Al of solid activating agent system 11.6kg is weighed, with metallocene ferrocene 0.186kg, that is, 1mol, mixing
Olefin polymerization catalysis is generated after reaction.
20. a kind of preparation method of olefin polymerization catalysis described in claim 16 comprising:
Solid activating agent system is prepared, step is as claimed in claim 15；
The i.e. 200mol Al of solid activating agent system 11.6kg is weighed, with metallocene ferrocene 0.186kg, that is, 1mol, mixing
Olefin polymerization catalysis is generated after reaction.
21. a kind of application as olefin polymerization catalysis comprising using described in claim 15 in olefin polymerization
Olefin polymerization catalysis.
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| CN201811114081.2A CN109369830A (en) | 2012-07-11 | 2012-07-11 | Solid activating agent system and preparation method thereof |
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