CN105906751B - A kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl - Google Patents
A kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl Download PDFInfo
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- CN105906751B CN105906751B CN201610348816.2A CN201610348816A CN105906751B CN 105906751 B CN105906751 B CN 105906751B CN 201610348816 A CN201610348816 A CN 201610348816A CN 105906751 B CN105906751 B CN 105906751B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/58—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with silicon, germanium, tin, lead, antimony, bismuth or compounds thereof
Abstract
The invention provides a kind of alkyl aluminum preparation method containing unsaturated chain alkyl, comprise the following steps：Rare earth compound, diolefin, alkyl aluminum compound and chloride are mixed, is reacted, obtains the alkyl aluminum containing unsaturated chain alkyl；The rare earth compound includes the one or more in rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate and alkoxy rare-earth；The diolefin includes butadiene and/or isoprene；The mol ratio of the diolefin and rare earth compound is (50~1000)：1；The temperature of the reaction is 0~80 DEG C；The time of the reaction is 2~12 hours.Compared to polymerization of the prior art, the drawbacks of present invention is reacted using in-situ method, and catalyst needs long time aging in polymerization before avoiding, have and simplify preparation technology, the advantages that shortening reaction time.
Description
Technical field
The invention belongs to polymer synthesis techniques field, more particularly to a kind of alkyl aluminum containing unsaturated chain alkyl
Preparation method.
Background technology
It is a kind of new polymerization to grow up in recent years to be coordinated chain transfer polymerization, has conventional anion activity poly
The advantages of conjunction, as polymer molecular weight is controllable and narrow molecular weight distribution, block copolymer can be prepared, polymer chain terminal can be carried out
Functional modification etc..What is more important, a plurality of polymer chain, center can be produced by being coordinated a central metal of chain transfer polymerization
Rate of metal reaches 100%.
Originally coordination chain transfer polymerization is mainly used in monoolefm polymerisations field, because it is excellent in terms of polymerization activity
Point, in recent years, coordination chain transfer polymerization also gradually receive the concern of people in diolefin field.Friebe etc. passes through power
Learn two kinds of typical alkyl aluminum (Al (iBu) of experimental study3,Al(iBu)2H) to the influence of polymer molecular weight, Al (i-Bu)2H chain transfer efficiency is Al (i-Bu)38 times, the chain transfer efficiencies of wherein Al-H parts is approximately Al-iBu parts chain tra nsfer effect
22 times of rate.Only has 1/3 Al (iBu) in course of reaction2H take part in chain transfer reaction (J.Macromol.Sci., Pure
Appl.Chem.2004；A41:245-256).Changchun Institute of Applied Chemistry reports Nd (vers)3/Al(iBu)2H/Me2SiCl2Catalytic body
System's catalysis isoprene carries out reversible coordination chain transfer polymerization, obtains high-cis-Isosorbide-5-Nitrae structure (96.5%), Narrow Molecular Weight Distribution
Polyisoprene, about 7 polymer chains can be produced on average each Nd atoms, wherein there is 6 polymer chains to be connected with Al, 1
Individual (J.Polym.Sci., the Part A that is connected with Nd:Polym.Chem.2010；48:4768-4774).Then it have studied Nd again
(OiPr)3/Al(iBu)2H/Me2SiCl2System Butadiene Polymerization, the polybutadiene of Narrow Molecular Weight Distribution is prepared, and it is flat
Each activated centre produces 6-8 bars polymer chain (Polymer, 2013,54,6716-6724), wherein an only Nd polymerization
Thing chain, remaining is Al polymer chains.It follows that by being coordinated in the polymer synthesized by chain transfer polymerization, it is most
Polymer chain is connected with Al, it is believed that formation is the chain alkyl aluminium containing unsaturated double-bond.
It is well known that played in alkene, diolefin coordination polymerization field alkyl aluminum as co-catalyst vital
Effect, especially in synthetic rubber field.At present, synthetic rubber industry formd with lithium system, transition metal systems (titanium system,
Cobalt system, nickel system etc.) and a variety of catalyst system and catalyzings that rare earth metal system (neodymium series etc.) etc. is major catalyst.And with rare-earth catalysis system
The polymer of synthesis turns into the focus of research due to having the characteristics that stereoregularity height, good linearity.Rare earth catalyst body at present
The composition of system is：The ternary catalyst systems that are formed with rare earth compound, alkyl aluminum and halide and with Rare Earth Complexes
With the binary catalyst system of alkyl aluminum composition.Alkyl aluminum compound is group essential in rare-earth catalysis system as can be seen here
Point, species, dosage and its substituent size of alkyl aluminum have a significant impact to rare earth catalyst diolefin polymerization.Wilson systems
Ground compares AlR3Straight chained alkyl aluminium (the Journal of Polymer Science Part A of type:Polymer
Chemistry,1995,33(14):2505–2513).It is relatively low even according to the methyl substituted catalyst activity of Wilson research
Without activity.Ethyl substitution can improve polymerization activity.Activity highest when propyl group and butyl substitute.Also, as substituent is empty
Between steric hindrance increase, the trend that cis- Isosorbide-5-Nitrae content is improved.It is embodied in active order：Aln-Pr3>>Aln-Dodec3=
Aln-Hex3=Aln-Oct3>Al(i-Bu)2H≈Al(i-Bu)3>AlEt3>>AlMe3.To cis- 1,4 content influence order be：
Al(i-Bu)3>Al(i-Bu)2H>Aln-Dodec3>Aln-Hex3=Aln-Oct3>AlEt3.Therefore the alkyl aluminum of large space steric hindrance
Compound can improve polybutadiene and the cis- Isosorbide-5-Nitrae content of polyisoprene to a certain extent, and then improve the mechanical property of rubber
Can, there is important potential using value.
At present, the alkyl aluminum containing unsaturated chain alkyl is prepared by way of polymerization mostly, first using rare earth chemical combination
Thing, alkyl aluminum compound, chloride and a small amount of diolefin are reacted, and are then aged reaction product, then will ageing
Product carries out catalytic polymerization with diolefin afterwards, obtains the double olefin copolymer that end group is aluminium, that is, contain unsaturated long alkane
The alkyl aluminum of base.But existing this preparation method needs to be aged for a long time, step is complicated, and time-consuming, influences
Production efficiency.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl, the present invention carries
The preparation method of confession simplifies the preparation process of chain alkyl aluminium.
The present invention provides a kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl, follows the steps below：
Rare earth compound, diolefin, alkyl aluminum compound are mixed with chloride, reacted, is obtained containing unsaturation
The alkyl aluminum of chain alkyl；
It is dilute that the rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate and alkoxy
One or more in soil；
The diolefin includes butadiene and/or isoprene；
The mol ratio of the diolefin and rare earth compound is (50~1000)：1；
The temperature of the reaction is 0~80 DEG C；
The time of the reaction is 2~12 hours.
Preferably, follow the steps below：
A) rare earth compound, diolefin and alkyl aluminum compound are mixed, is reacted, obtains midbody product；
B) midbody product is mixed with chloride, reacted, obtains the alkyl containing unsaturated chain alkyl
Aluminium.
Preferably, the alkyl aluminum compound includes trialkylaluminium and/or alkyl aluminium hydride.
Preferably, the chloride include a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium ethide, tertiary butyl chloride,
One kind in benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane and silicon tetrachloride or
It is several.
Preferably, the rare earth compound includes neodymium caprate, neodymium iso-octanate, lanthanum naphthenate, (2- ethylhexyls) sour neodymium,
(2- ethylhexyls) phosphonic acids neodymium list -2- ethylhexyl esters, ethyoxyl neodymium, positive propoxy neodymium, isopropoxy lanthanum, isobutoxy shirt, uncle
One or more in butoxy neodymium and different octyloxy neodymium.
Preferably, the step A) in reaction time be 0.1~2 hour；
The step A) in reaction temperature be 0~80 DEG C.
Preferably, the step B) in reaction time be 2~10 hours；
The step B) in reaction temperature be 20~80 DEG C.
Preferably, the mol ratio of the alkyl aluminum compound and rare earth compound is (10~60)：1.
Preferably, the mol ratio of the chloride and rare earth compound is (1~3)：1.
The invention provides a kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl, comprise the following steps：Will
Rare earth compound, diolefin, alkyl aluminum compound and chloride mixing, are reacted, are obtained containing unsaturated chain alkyl
Alkyl aluminum；The rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate and alkoxy rare-earth
In one or more；The diolefin includes butadiene and/or isoprene；Mole of the diolefin and rare earth compound
Than for (50~1000)：1；The temperature of the reaction is 0~80 DEG C；The time of the reaction is 2~12 hours.Compared to existing
Polymerization in technology, the present invention are reacted using in-situ method, and catalyst needs long-time old in polymerization before avoiding
The drawbacks of change, reacted after only raw material need to be mixed, simplify preparation process, shorten technological process, and react
The time of consuming is shorter.
Embodiment
The invention provides a kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl, comprise the following steps：
Rare earth compound, diolefin, alkyl aluminum compound are mixed with chloride, reacted, is obtained containing unsaturation
The alkyl aluminum of chain alkyl；
It is dilute that the rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate and alkoxy
Soil；
The diolefin includes butadiene and/or isoprene；
The mol ratio of the diolefin and rare earth compound is (50~1000)：1；
The temperature of the reaction is 0~80 DEG C；
The time of the reaction is 2~12 hours.
The present invention preferably mixes rare earth compound, diolefin and alkyl aluminum compound, is reacted, and obtains intermediate production
Thing；
The midbody product is mixed with chloride, reacted, obtains the alkyl aluminum containing unsaturated chain alkyl.
In the present invention, the rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate
And alkoxy rare-earth；Preferably include neodymium caprate Nd (vers)3, neodymium iso-octanate Nd (EHA)3, lanthanum naphthenate La (naph)3、(2-
Ethylhexyl) sour neodymium Nd (P204)3, (2- ethylhexyls) phosphonic acids neodymium list -2- ethylhexyl ester Nd (P507)3, ethyoxyl neodymium, positive third oxygen
One or more in base neodymium, isopropoxy lanthanum, isobutoxy shirt, tert-butoxy neodymium and different octyloxy neodymium.
In the present invention, the diolefin includes conjugated diolefin, preferably includes butadiene and/or isoprene；It is described
The mol ratio of diolefin and rare earth compound is (50~1000)：1, be preferably (100~900)：1, more preferably (200~
800)：1, specifically, can be 400 in an embodiment of the present invention:1 or 500:1.
In the present invention, the alkyl aluminum compound preferably includes trialkylaluminium and/or alkyl aluminium hydride, more preferably includes
Triisobutyl aluminium, trioctylaluminum, dimethyl hydrogenated aluminium, diisobutylaluminium hydride, diethylaluminum hydride, di-n-butyl aluminum hydride,
One kind in diisopropyl aluminum hydride, di-n-hexyl aluminum hydride, dicyclohexyl aluminum hydride, di-n-octyl aluminum hydride and triethyl aluminum
It is or several；The mol ratio of the alkyl aluminum compound and rare earth compound is preferably (10~60)：1, more preferably (20~50)：
1, specifically, can be 40 in an embodiment of the present invention:1.
In the present invention, the chloride preferably include a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium ethide,
In tertiary butyl chloride, benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane and silicon tetrachloride
One or more；The mol ratio of the chloride and rare earth compound is preferably (1~3)：1, more preferably 2:1.
In the present invention, the total time for preparing the alkyl aluminum containing unsaturated chain alkyl is preferably 2~12 small
When, the reaction time for preparing the midbody product is preferably 0~2 hour, more preferably 0.1~2 hour, most preferably 0.25
~1 hour；The reaction temperature for preparing the midbody product is preferably 0~80 DEG C, more preferably 20~60 DEG C, most preferably 30
~50 DEG C, specifically, can be 20 DEG C, 50 DEG C or 60 DEG C in an embodiment of the present invention；Prepared and contained by the midbody product
The time for having the reaction of the alkyl aluminum of unsaturated chain alkyl is preferably 2~10 hours, more preferably 3~9 hours, is most preferably
4~8 hours, specifically, can be 5 hours, 7 hours or 8 hours；Prepared by the midbody product containing unsaturated long alkane
The temperature of the reaction of the alkyl aluminum of base is preferably 20~80 DEG C, more preferably 30~60 DEG C, specifically, can be 20 DEG C, 50 DEG C
Or 60 DEG C.
The present invention carries out the preparation of the alkyl aluminum containing unsaturated chain alkyl preferably under protective gas atmosphere.
The invention provides a kind of alkyl aluminum preparation method containing unsaturated chain alkyl, comprise the following steps：Will be dilute
Earth compounds, diolefin, alkyl aluminum compound and chloride mixing, are reacted, obtain the alkane containing unsaturated chain alkyl
Base aluminium；The mol ratio of the diolefin and rare earth compound is (50~1000)：1；The temperature of the reaction is 0~80 DEG C；Institute
The time for stating reaction is 2~12 hours.Compared to polymerization of the prior art, the present invention is reacted using in-situ method, nothing
Need to be aged, reacted after only raw material need to be mixed, simplify preparation process, shorten technological process, and react consumption
The time taken is shorter.Also, the preparation method yield of the present invention is higher, can reach 100%, what is obtained contains unsaturated long-chain
For the molecular weight distribution of the alkyl aluminum of alkyl between 1.22~2.01, the polymer chain number of average each active neutral is 3~8.
In order to further illustrate the present invention, unsaturated long alkane is contained to one kind provided by the invention with reference to embodiments
The preparation method of the alkyl aluminum of base is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1~4
Under nitrogen protection, A, B and C are sequentially added into dry polymer reactor, wherein B component is butadiene, B
Mol ratio with A is 50:1, C and A mol ratio is 10:1, reacted 2 hours at 0 DEG C, add D, wherein D and A mol ratio
For 2:1, reacted 5 hours at 50 DEG C.1 is the results are shown in Table, table 1 is the raw material and result data of the embodiment of the present invention 1~4.
The raw material and result data of the embodiment of the present invention 1~4 of table 1
Polymer chain number caused by average each activated centre, Np=B/A × 54 × Yield/Mn, wherein, B/A is substance B
With the mol ratio of substance A, Yield is yield, MnFor molecular weight, Mw/MnFor molecular weight distribution.
Embodiment 5~7
Under nitrogen protection, into dry polymer reactor, A, B, C and D are sequentially added, wherein B component is isoamyl two
Alkene, B and A mol ratio are 200:1, C and A mol ratio is 60:1, D and A mol ratio is 1:1, it is small that 7 are reacted at 80 DEG C
When.2 are the results are shown in Table, table 2 is the raw material and result data of the embodiment of the present invention 5~7.
The raw material and result data of the embodiment of the present invention 5~7 of table 2
Polymer chain number caused by average each activated centre, Np=B/A × 68 × Yield/Mn, wherein, B/A is substance B
With the mol ratio of substance A, Yield is yield.
Embodiment 8~11
Under nitrogen protection, A, B and C are sequentially added into dry polymer reactor, wherein B component is butadiene, B
Mol ratio with A is 500:1, C and A mol ratio is 40:1, reacted 1 hour at 50 DEG C, add D, wherein D and A mole
Than for 3:1, reacted 10 hours at 20 DEG C.3 are the results are shown in Table, table 3 is the raw material and result data of the embodiment of the present invention 8~11.
The raw material and result data of the embodiment of the present invention 8~11 of table 3
Polymer chain number caused by average each activated centre, Np=B/A × 54 × Yield/Mn, wherein, B/A is substance B
With the mol ratio of substance A, Yield is yield.
Embodiment 12~15
Under nitrogen protection, A, B and C are sequentially added into dry polymer reactor, wherein B component is butadiene, B
Mol ratio with A is 1000:1, C and A mol ratio is 20:1,15 points are reacted at 80 DEG C, adds D, wherein D and A mole
Than for 3:1, reacted 8 hours at 60 DEG C.4 are the results are shown in Table, table 4 is the raw material and result data of the embodiment of the present invention 12~15.
The raw material and result data of the embodiment of the present invention 12~15 of table 4
Polymer chain number caused by average each activated centre, Np=B/A × 54 × Yield/Mn, wherein, B/A is substance B
With the mol ratio of substance A, Yield is yield.
Embodiment 16~18
Under nitrogen protection, into dry polymer reactor, A, B and C are sequentially added, wherein B component is isoprene,
B and A mol ratio is 400:1, C and A mol ratio is 20:1,20 points are reacted at 50 DEG C, adds D, wherein D and A mole
Than for 3:1, reacted 8 hours at 60 DEG C.5 are the results are shown in Table, table 5 is the raw material and result data of the embodiment of the present invention 16~18.
The raw material and result data of the embodiment of the present invention 16~18 of table 5
Polymer chain number caused by average each activated centre, Np=B/A × 68 × Yield/Mn, wherein, B/A is substance B
With the mol ratio of substance A, Yield is yield.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of the alkyl aluminum containing unsaturated chain alkyl, is carried out in accordance with the following methods：
A) rare earth compound, diolefin and alkyl aluminum compound are mixed, is reacted, obtains midbody product；
The step A) in reaction time be 0.1~2 hour；
The step A) in reaction temperature be 0~80 DEG C；
B) midbody product is mixed with chloride, reacted, obtains the alkyl aluminum containing unsaturated chain alkyl；
The step B) in reaction time be 2~10 hours；
The step B) in reaction temperature be 20~80 DEG C；
The rare earth compound is included in rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate and alkoxy rare-earth
One or more；
The diolefin includes butadiene and/or isoprene；
The mol ratio of the diolefin and rare earth compound is (50~1000)：1.
2. preparation method according to claim 1, it is characterised in that the alkyl aluminum compound include trialkylaluminium and/
Or alkyl aluminium hydride.
3. preparation method according to claim 1, it is characterised in that the chloride includes a chloro-di-isobutyl aluminum, one
Chlorodiethyl aluminium, sesquialter aluminium ethide, tertiary butyl chloride, benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyldichlorosilane, three
One or more in methylchlorosilane and silicon tetrachloride.
4. preparation method according to claim 1, it is characterised in that the rare earth compound includes neodymium caprate, different pungent
Sour neodymium, lanthanum naphthenate, (2- ethylhexyls) sour neodymium, (2- ethylhexyls) phosphonic acids neodymium list -2- ethylhexyl esters, ethyoxyl neodymium, positive third
One or more in epoxide neodymium, isopropoxy lanthanum, isobutoxy shirt, tert-butoxy neodymium and different octyloxy neodymium.
5. preparation method according to claim 1, it is characterised in that the alkyl aluminum compound and rare earth compound rub
Your ratio is (10~60)：1.
6. preparation method according to claim 1, it is characterised in that the mol ratio of the chloride and rare earth compound is
(1~3)：1.
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