CN103880872A - Preparation method and application of lactic acid rare earth complex and rare earth catalyst - Google Patents
Preparation method and application of lactic acid rare earth complex and rare earth catalyst Download PDFInfo
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Abstract
The invention provides a preparation method and application of a lactic acid rare earth complex and a rare earth catalyst. The preparation method of the rare earth catalyst comprises the following steps: under the condition of inert gas shielding, mixing the lactic acid rare earth complex, alkyl aluminum, the first diolefin, alkyl aluminum chloride and the second organic solvent, and ageing to obtain a rare earth catalyst. In comparison with the existing diolefin catalyst, the preparation method of the rare earth catalyst is simple, dehydration is not needed, and the reaction condition is not required rigorously. Meanwhile, lactic acid is reagent widely used in the chemical industry, is wide in source, low in cost, convenient to transport and easy to store.
Description
Technical field
The invention belongs to catalyst technical field, relate in particular to lactic acid rare earth compounding, rare earth catalyst and preparation method thereof and application.
Background technology
The research of rare earth catalyst double olefin copolymer be last century the fifties grow up, compared with being catalyst system with traditional lithium (Li), titanium (Ti), chromium (Co) and nickel (Ni), have the following advantages: initiator activity is high, consumption is few, and is easy to dispersed; Initiator residue is harmless to rubber performance, without through washing deliming, three wastes treatment capacity is few; Polymer performance temperature influence is less, owing to adopting higher temperature of reaction, is conducive to polymeric kettle heat conduction; In production process, do not need to wash deliming, simplified technical process; Reduce production cost.Through the development of over half a century, rare-earth catalysis system has been established the three-way catalyst system forming with rare-earth salts, aluminum alkyls and halogenide and the binary catalyst system forming with Rare Earth Complexes and aluminum alkyls.
The main component that industrialization is at present used is ternary RE catalyst system, and although binary rare-earth catalyst system also possesses higher catalytic activity, but the complicated process of preparation of Rare Earth Complexes, complex operation, the technical parameters such as temperature of reaction, time, pressure are required harsh, time-consuming, improve the preparation cost of catalyzer; Although the rare earth carboxylate in ternary RE system is soluble in saturated hydrocarbon solution, there is higher catalytic activity, the preparation cost of this catalyzer is still higher.Along with the development of market economy, the fierceness day by day of competition, how to reduce production costs and become the task of top priority that enterprise need to solve, therefore concerning being engaged in the scientific research personnel of the industry, have higher requirement: the existing catalyst system of Improvement and perfection and need to develop new catalyst system.
Lactic acid is the reagent that chemical industry is generally used, wide material sources, cheap, be convenient to transport, be easy to storage.The simple molecular structure of lactic acid, and simultaneously contain in molecule-CH
3,-OH ,-COOH, become the synthesis material of a lot of chemical substances.In addition, lactic acid at macromolecular material, catalysis, life organic and environment etc. many-sided developed.In structure aspects, the existing a lot of reports of the title complex of lactic acid and main group metal and transition metal, the simple molecular structure of lactic acid, and Sauerstoffatom proportion is larger, and therefore it can while and multiple metallic ion coordination.In addition, lactic acid metal complexes can also very perfectly embody optical, electrical, magnetic and the catalytic performance of metal ion.
The present invention considers to prepare the polyreaction of lactic acid rare earth compounding for diolefin.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide lactic acid rare earth compounding, rare earth catalyst and preparation method thereof and application, and this lactic acid rare earth compounding can be used for the polyreaction of catalysis diolefin.
The invention provides a kind of lactic acid rare earth compounding, as shown in the formula (I):
Ln（C
3H
5O
3）
3·xL （I）；
Wherein, Ln is rare earth element; L is to electronics part; 0 < x≤4.
Preferably, described L is alcohol compound, sulfoxide compound, aminated compounds or ester compound.
Preferably, described alcohol compound is Virahol, isooctyl alcohol, hexalin or phenylcarbinol; Described sulfoxide compound is dimethyl sulfoxide (DMSO) or diphenyl sulfoxide.
Preferably, described aminated compounds is diethylamine, triethylamine, n-Butyl Amine 99 or DMF.
Preferably, described ester compound is TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
The preparation method who the invention provides a kind of lactic acid rare earth compounding, comprises the following steps:
Lactic acid rare earth compound is mixed in the first organic solvent with giving electronics part, and back flow reaction is carried out in heating, removes after the first organic solvent, obtains lactic acid rare earth compounding.
The present invention also provides a kind of preparation method of rare earth catalyst, comprising:
Under the condition of protection of inert gas, lactic acid rare earth compounding, aluminum alkyls, the first diolefin, alkyl aluminum chloride are mixed with the second organic solvent, ageing, obtains rare earth catalyst.
Preferably, the mol ratio of the rare earth element in described lactic acid rare earth compounding and aluminum alkyls is 1:(10～60); Rare earth element in described lactic acid rare earth compounding and the mol ratio of alkyl aluminum chloride are 1:(1～4).
Preferably, the mol ratio of the rare earth element in described lactic acid rare earth compounding and the first diolefin is 1:(5～20).
The present invention also provides a kind of application of rare earth catalyst, it is characterized in that, comprising:
The second diolefin, the second organic solvent are mixed with rare earth catalyst, react, obtain diolefin multipolymer.
The invention provides a kind of lactic acid rare earth compounding, rare earth catalyst and preparation method thereof and application; the preparation method of this rare earth catalyst is: under the condition of protection of inert gas; lactic acid rare earth compounding, aluminum alkyls, the first diolefin, alkyl aluminum chloride are mixed with the second organic solvent; ageing, obtains rare earth catalyst.Compared with existing diolefin catalyzer, rare earth catalyst preparation method of the present invention is simple, without dewatering, and reaction conditions is not had to harsh requirement; Meanwhile, lactic acid is the reagent that chemical industry is generally used, wide material sources, cheap, be convenient to transport, be easy to storage.
Embodiment
The invention provides a kind of rare earth compounding, as shown in the formula (I):
Ln（C
3H
5O
3）
3·xL （I）；
Wherein, Ln is rare earth element, and described rare earth element is rare earth element well known to those skilled in the art, there is no special restriction, is preferably La, Nd, Sm, Er or Yb in the present invention; L is to electronics part, is preferably alcohol compound, sulfoxide compound, aminated compounds or ester compound in the present invention; 0 < x≤4, are preferably 1～4 integer.
In the present invention, described alcohol compound is preferably Virahol, isooctyl alcohol, hexalin or phenylcarbinol; Described sulfoxide compound is preferably dimethyl sulfoxide (DMSO) or diphenyl sulfoxide; Described aminated compounds is preferably diethylamine, triethylamine, n-Butyl Amine 99 or DMF; Described ester compound is preferably TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
The present invention also provides a kind of preparation method of lactic acid rare earth compounding, comprises the following steps:
Lactic acid rare earth compound is mixed in the first organic solvent with giving electronics part, and back flow reaction is carried out in heating, removes after the first organic solvent, obtains lactic acid rare earth compounding.
Wherein, the present invention does not have special restriction to the source of all raw materials, for commercially available or self-control all can.
Described lactic acid rare earth compound is preferably prepared according to following steps: lactic acid is reacted with rare-earth hydroxide, obtain lactic acid rare earth compound.
Lactic acid is reacted with rare-earth hydroxide, wherein, described rare-earth hydroxide is rare-earth hydroxide well known to those skilled in the art, there is no special restriction, and the present invention is preferably lanthanum hydroxide, neodymium hydroxide Neodymium trihydroxide, samaric hydroxide, erbium hydroxide or ytterbium hydroxide; Described rare-earth hydroxide can be and commercially availablely also can be homemadely, and the present invention is preferably prepared in accordance with the following methods: rare earth oxide is reacted with mixed in hydrochloric acid, remove excessive hydrochloric acid, add successively again water and ammoniacal liquor, complete to rare-earth precipitation, filter, washing, obtains rare-earth hydroxide.The mol ratio of described rare earth oxide and hydrochloric acid is preferably 1:(1～1.5), more preferably 1:1.
Lactic acid reacts with rare-earth hydroxide, this reactions steps is preferably specially: rare-earth hydroxide is mixed with water, obtain rare-earth hydroxide suspension, under constantly stirring, lactic acid aqueous solution is dropped in rare-earth hydroxide suspension, lactic acid reacts with rare-earth hydroxide, obtains lactic acid rare earth compound.The temperature that lactic acid reacts with rare-earth hydroxide is preferably 60 DEG C～70 DEG C; Reaction times is preferably 3.5～4.5h; After having reacted, preferably excessive aqueous solvent is removed in evaporation, and product is separated out, and filters, and after being dried, obtains lactic acid rare earth compound; Described evaporation preferably adopts the mode of atmospheric evaporation at 45 DEG C.
Described lactic acid rare earth compound is mixed in the first organic solvent with giving electronics part, and wherein, the described electronics part of giving is same as above, does not repeat them here; Described lactic acid rare earth compound is preferably 1:x, described 0 < x≤4 with the mol ratio of giving electronics part; Described the first organic solvent is ability organic solvent known by the technical staff, there is no special restriction, is preferably tetrahydrofuran (THF) in the present invention.
After mixing, back flow reaction is carried out in heating, and the time of described back flow reaction is preferably 5～24h; After reaction, remove the first organic solvent, obtain lactic acid rare earth compounding.
The present invention also provides and has adopted above-mentioned lactic acid rare earth compounding to prepare the method for rare earth catalyst; comprise: under the condition of protection of inert gas; lactic acid rare earth compounding, aluminum alkyls, the first diolefin, alkyl aluminum chloride are mixed with the second organic solvent, and ageing, obtains rare earth catalyst.
According to the present invention, under the condition of protection of inert gas, lactic acid rare earth compounding, aluminum alkyls, the first diolefin, alkyl aluminum chloride are mixed with the second organic solvent, wherein said rare gas element is rare gas element well known to those skilled in the art, there is no special restriction, in the present invention, be preferably nitrogen; Described aluminum alkyls is aluminum alkyls well known to those skilled in the art, there is no special restriction, in the present invention, be preferably trialkylaluminium and/or alkyl-al hydride, more preferably one or more in diisobutylaluminium hydride, ADEH, triisobutyl aluminium and triethyl aluminum; The mol ratio of described aluminum alkyls and lactic acid rare earth compounding rare earth elements is preferably (10～60): 1, and more preferably (20～40): 1; Described alkyl aluminum chloride is preferably one or more in diisobutyl aluminum chloride, aluminium diethyl monochloride and sesquialter ethyl aluminum chloride; The mol ratio of described alkyl aluminum chloride and lactic acid rare earth compounding rare earth elements is preferably (1～4): 1, and more preferably (2～3): 1; Described the first diolefin is diolefin well known to those skilled in the art, there is no special restriction, is preferably divinyl and/or isoprene in the present invention; The mol ratio of described the first diolefin and lactic acid rare earth compounding rare earth elements is preferably (5～20): 1, and more preferably (10～15): 1; Described the second organic solvent is organic solvent well known to those skilled in the art, there is no special restriction, is preferably hexane in the present invention; The amount that described the second organic solvent adds is preferably and makes the concentration of lactic acid rare earth compounding rare earth elements is 2 × 10
-5～5 × 10
-5, more preferably 3 × 10
-5～4 × 10
-5.
After above-mentioned raw materials is mixed, ageing, obtains rare earth catalyst.Wherein, the temperature of described ageing is preferably 0 DEG C～70 DEG C, more preferably 50 DEG C～70 DEG C; The temperature of described ageing is preferably 1～24h, more preferably 5～20h.
Rare earth catalyst preparation method of the present invention is simple, without dewatering, and reaction conditions is not had to harsh requirement; Meanwhile, lactic acid is the reagent that chemical industry is generally used, wide material sources, cheap, be convenient to transport, be easy to storage.
The present invention also provides a kind of application method of rare earth catalyst of above-mentioned preparation, comprising: the second diolefin, the second organic solvent are mixed with rare earth catalyst, react, obtain diolefin multipolymer.
Described the second double olefin compound is diolefin well known to those skilled in the art, there is no special restriction, is preferably divinyl and/or isoprene in the present invention; Described the second organic solvent is same as above, again repeats no more.Described rare earth catalyst rare earth elements mole be preferably 1 × 10 with the mass ratio of the second diolefin
-6～8 × 10
-6mol/g, more preferably 4 × 10
-6～6 × 10
-6mol/g.
The second diolefin, the second organic solvent are mixed with rare earth catalyst, react.The temperature of described reaction is preferably 0 DEG C～70 DEG C, more preferably 50 DEG C～70 DEG C; The time of described reaction is preferably 1～24h, more preferably 8～20h.
According to the present invention, after having reacted, preferably use the ethanolic soln termination reaction of BHT, the ethanolic soln termination reaction of the BHT that is more preferably 1%～3% with massfraction; And then precipitate in ethanol, after washing with alcohol extruding, vacuum-drying, obtains diolefin multipolymer.
In order to further illustrate the present invention, below in conjunction with embodiment, lactic acid rare earth compounding provided by the invention, rare earth catalyst and preparation method thereof are described in detail with application.
In following examples, reagent used is commercially available.
Embodiment 1
1.1 by Neodymium trioxide and hydrochloric acid according to mol ratio 1:1 hybrid reaction, then steam excessive hydrochloric acid, add water, make the aqueous solution, then add ammoniacal liquor complete to rare-earth precipitation, filter, be washed to without chlorion, obtain neodymium hydroxide Neodymium trihydroxide.
1.2 mix the neodymium hydroxide Neodymium trihydroxide obtaining in 1.1 with water, obtain suspension, are heated to 60 DEG C, under constantly stirring, lactic acid aqueous solution is dropped in suspension, and after reaction 4h, the excessive aqueous solvent of atmospheric evaporation at 45 DEG C, separates out product, filter, dry, obtain lactic acid neodymium compound.
1.3 is 1:2 by the lactic acid neodymium compound obtaining in 1.2 and isooctyl alcohol according to mol ratio, and ratio is added in reactor, add 40ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Nd (C
3h
5o
3)
33 (CH
3)
2c (CH
2)
5oH.
Embodiment 2
The ratio that is 1:3 according to mol ratio by the lactic acid neodymium compound obtaining in 1.2 and ethamine is added in reactor, add 20ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Nd (C
3h
5o
3)
33CH
3cH
2nH
2.
Embodiment 3
The ratio that is 1:3 according to mol ratio by the lactic acid neodymium compound obtaining in 1.2 and TRI N BUTYL PHOSPHATE (TBP) is added in reactor, add again 80ml tetrahydrofuran (THF) as solvent, condensing reflux 5～24h under boiling state, boil off solvent, and be dried to constant weight, obtain lactic acid rare earth compounding Nd (C
3h
5o
3)
33TBP.
Embodiment 4
4.1 by lanthanum trioxide and hydrochloric acid according to mol ratio 1:1 hybrid reaction, then steam excessive hydrochloric acid, add water, make the aqueous solution, then add ammoniacal liquor complete to rare-earth precipitation, filter, be washed to without chlorion, obtain lanthanum hydroxide.
4.2 mix the lanthanum hydroxide obtaining in 4.1 with water, obtain suspension, are heated to 60 DEG C, under constantly stirring, lactic acid aqueous solution is dropped in suspension, and after reaction 4h, the excessive aqueous solvent of atmospheric evaporation at 45 DEG C, separates out product, filter, dry, obtain lactic acid lanthanum compound.
4.3 is 1:3 by the lactic acid lanthanum compound obtaining in 4.2 and hexalin according to mol ratio, and ratio is added in reactor, add 40ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding La (C
3h
5o
3)
33
Embodiment 5
The ratio that is 1:3 according to mol ratio by the lactic acid lanthanum compound obtaining in 4.2 and dimethyl sulfoxide (DMSO) is added in reactor, add 60ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding La (C
3h
5o
3)
33
Embodiment 6
The ratio that is 1:2 according to mol ratio by the lactic acid lanthanum compound obtaining in 4.2 and diethylamine is added in reactor, add 20ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding La (C
3h
5o
3)
32 (CH
3cH
2)
2nH.
Embodiment 7
The ratio that is 1:3 according to mol ratio by the lactic acid lanthanum compound obtaining in 4.2 and triphenylphosphate (TPP) is added in reactor, add again 80ml tetrahydrofuran (THF) as solvent, condensing reflux 5～24h under boiling state, boil off solvent, and be dried to constant weight, obtain lactic acid rare earth compounding La (C
3h
5o
3)
33TPP.
Embodiment 8
8.1 by Samarium trioxide and hydrochloric acid according to mol ratio 1:1 hybrid reaction, then steam excessive hydrochloric acid, add water, make the aqueous solution, then add ammoniacal liquor complete to rare-earth precipitation, filter, be washed to without chlorion, obtain samaric hydroxide.
8.2 mix the samaric hydroxide obtaining in 8.1 with water, obtain suspension, are heated to 60 DEG C, under constantly stirring, lactic acid aqueous solution is dropped in suspension, and after reaction 4h, the excessive aqueous solvent of atmospheric evaporation at 45 DEG C, separates out product, filter, dry, obtain lactic acid samarium compound.
8.3 is 1:3 by the lactic acid samarium compound obtaining in 8.2 and triethylamine according to mol ratio, and ratio is added in reactor, add 20ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Sm (C
3h
5o
3)
33 (CH
3cH
2)
3n.
Embodiment 9
The ratio that is 1:2 according to mol ratio by the lactic acid samarium compound obtaining in 8.2 and diisobutyl phthalate (DBP) is added in reactor, add again 80ml tetrahydrofuran (THF) as solvent, condensing reflux 5～24h under boiling state, boil off solvent, and be dried to constant weight, obtain lactic acid rare earth compounding Sm (C
3h
5o
3)
32DBP.
Embodiment 10
10.1 by Erbium trioxide and hydrochloric acid according to mol ratio 1:1 hybrid reaction, then steam excessive hydrochloric acid, add water, make the aqueous solution, then add ammoniacal liquor complete to rare-earth precipitation, filter, be washed to without chlorion, obtain erbium hydroxide.
10.2 mix the erbium hydroxide obtaining in 10.1 with water, obtain suspension, are heated to 60 DEG C, under constantly stirring, lactic acid aqueous solution is dropped in suspension, and after reaction 4h, the excessive aqueous solvent of atmospheric evaporation at 45 DEG C, separates out product, filter, dry, obtain lactic acid erbium compound.
10.3 is 1:3 by the lactic acid erbium compound obtaining in 10.2 and Virahol according to mol ratio, and ratio is added in reactor, add 40ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Er (C
3h
5o
3)
33 (CH
3)
2cHOH.
Embodiment 11
By the lactic acid erbium compound and the N that obtain in 10.2, the ratio that dinethylformamide is 1:3 according to mol ratio is added in reactor, add again 20ml tetrahydrofuran (THF) as solvent, condensing reflux 5～24h under boiling state, boil off solvent, and be dried to constant weight, obtain lactic acid rare earth compounding Er (C
3h
5o
3)
33C
3h
7nO.
Embodiment 12
12.1 by ytterbium oxide and hydrochloric acid according to mol ratio 1:1 hybrid reaction, then steam excessive hydrochloric acid, add water, make the aqueous solution, then add ammoniacal liquor complete to rare-earth precipitation, filter, be washed to without chlorion, obtain ytterbium hydroxide.
12.2 mix the ytterbium hydroxide obtaining in 12.1 with water, obtain suspension, are heated to 60 DEG C, under constantly stirring, lactic acid aqueous solution is dropped in suspension, and after reaction 4h, the excessive aqueous solvent of atmospheric evaporation at 45 DEG C, separates out product, filter, dry, obtain lactic acid ytterbium compound.
12.3 is 1:3 by the lactic acid ytterbium compound obtaining in 12.2 and phenylcarbinol according to mol ratio, and ratio is added in reactor, add 40ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Yb (C
3h
5o
3)
33
Embodiment 13
The ratio that is 1:3 according to mol ratio by the lactic acid ytterbium compound obtaining in 12.2 and diphenyl sulfoxide is added in reactor, add 60ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Yb (C
3h
5o
3)
33
Embodiment 14
The ratio that is 1:4 according to mol ratio by the lactic acid ytterbium compound obtaining in 12.2 and n-Butyl Amine 99 is added in reactor, add 20ml tetrahydrofuran (THF) as solvent, under boiling state, condensing reflux 5～24h, boils off solvent again, and be dried to constant weight, obtain lactic acid rare earth compounding Yb (C
3h
5o
3)
34CH
3(CH
2)
2nH
2.
Embodiment 15
The ratio that is 1:3 according to mol ratio by the lactic acid ytterbium compound obtaining in 12.2 and dioctyl phthalate (DOP) (DOP) is added in reactor, add again 80ml tetrahydrofuran (THF) as solvent, condensing reflux 5～24h under boiling state, boil off solvent, and be dried to constant weight, obtain lactic acid rare earth compounding Yb (C
3h
5o
3)
33DOP.
Embodiment 16～18
Under the condition of nitrogen protection, in dry catalyst preparation pipe, add successively 1 × 10
-4the AlEt of the 2.0mol/L of mol lactic acid rare earth compounding, 0.5ml
3the Al (i-Bu) of the 2.0mol/L of hexane solution, 0.1ml
2the isoprene hexane solution of the 2.0mol/L of Cl hexane solution and 0.5ml, wherein the kind of lactic acid rare earth compounding is in table 1, the mol ratio of triethyl aluminum and lactic acid rare earth compounding rare earth elements is 10:1, the mol ratio of diisobutyl aluminum chloride and lactic acid rare earth compounding rare earth elements is 2:1, the mol ratio of isoprene and lactic acid rare earth compounding rare earth elements is 10:1, add 0.9ml hexane, the concentration that makes solution rare earth elements is 5 × 10
-5mol/ml, at 50 DEG C, ageing 5 hours, obtains rare earth catalyst.
Under the condition of nitrogen protection, be 10g/100ml isoprene hexane solution to adding 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free, then add rare earth catalyst, the mole number of rare earth catalyst rare earth elements and the mass ratio of isoprene are 8 × 10
-6mol/g, be heated to 50 DEG C of reaction 10h, then with condensing polymkeric substance containing the ethanol of massfraction 1% antioxidant 264, after washing is pushed, 40 DEG C of vacuum-dryings, to constant weight, obtains polyisoprene.
The polyisoprene obtaining is analyzed, obtained experimental result in table 1.
Raw materials used and experimental result in table 1 embodiment 16～18
Embodiment 19～22
Under the condition of nitrogen protection, in dry catalyst preparation pipe, add successively 1 × 10
-4the Al (i-Bu) of the 2.0mol/L of mol lactic acid rare earth compounding, 1ml
3the AlEt of the 2.0mol/L of hexane solution, 0.15ml
2the isoprene hexane solution of the 2.0mol/L of Cl hexane solution and 1ml, wherein the kind of lactic acid rare earth compounding is in table 2, the mol ratio of triisobutyl aluminium and lactic acid rare earth compounding rare earth elements is 20:1, the mol ratio of aluminium diethyl monochloride and lactic acid rare earth compounding rare earth elements is 3:1, the mol ratio of isoprene and lactic acid rare earth compounding rare earth elements is 20:1, add 0.35ml hexane, the concentration that makes solution rare earth elements is 4 × 10
-5mol/ml, at 0 DEG C, ageing 24 hours, obtains rare earth catalyst.
Under the condition of nitrogen protection, be 10g/100ml divinyl hexane solution to adding 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free, then add rare earth catalyst, the mole number of rare earth catalyst rare earth elements and the mass ratio of divinyl are 6 × 10
-6mol/g, be heated to 70 DEG C of reaction 8h, then with condensing polymkeric substance containing the ethanol of massfraction 1% antioxidant 264, after washing is pushed, 40 DEG C of vacuum-dryings, to constant weight, obtains polyhutadiene.
The polyhutadiene obtaining is analyzed, obtained experimental result in table 2.
Raw materials used and experimental result in table 2 embodiment 19～22
Embodiment 23～26
Under the condition of nitrogen protection, in dry catalyst preparation pipe, add successively 1 × 10
-4the AlEt of the 2.0mol/L of mol lactic acid rare earth compounding, 2ml
2the AlEt of the 2.0mol/L of H hexane solution, 0.17ml
2the isoprene hexane solution of the 2.0mol/L of Cl hexane solution and 0.5ml, wherein the kind of lactic acid rare earth compounding is in table 3, the mol ratio of ADEH and lactic acid rare earth compounding rare earth elements is 40:1, the mol ratio of aluminium diethyl monochloride and lactic acid rare earth compounding rare earth elements is 1:1, the mol ratio of isoprene and lactic acid rare earth compounding rare earth elements is 10:1, add 2.33ml hexane, the concentration that makes solution rare earth elements is 2 × 10
-5mol/ml, at 70 DEG C, ageing 10 hours, obtains rare earth catalyst.
Under the condition of nitrogen protection; be 10g/100ml butadiene-isoprene hexane solution to adding 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free; wherein the mass ratio of divinyl and isoprene is 4:1; then add rare earth catalyst, the mole number of rare earth catalyst rare earth elements and the mass ratio of butadiene-isoprene are 1 × 10
-6mol/g, in 0 DEG C of reaction 24h, then with condensing polymkeric substance containing the ethanol of massfraction 1% antioxidant 264, after washing is pushed, 40 DEG C of vacuum-dryings, to constant weight, obtain butadiene isoprene copolymer.
The butadiene isoprene copolymer obtaining is analyzed, obtained experimental result in table 3.
Raw materials used and experimental result in table 3 embodiment 23～26
Embodiment 27～30
Under the condition of nitrogen protection, in dry catalyst preparation pipe, add successively 1 × 10
-4the Al (i-Bu) of the 2.0mol/L of mol lactic acid rare earth compounding, 3ml
2the AlEt of the 2.0mol/L of H hexane solution, 0.1ml
2the divinyl hexane solution of the 2.0mol/L of Cl hexane solution and 0.25ml, wherein the kind of lactic acid rare earth compounding is in table 4, the mol ratio of diisobutylaluminium hydride and lemon lactic acid rare earth compounding rare earth elements is 60:1, the mol ratio of aluminium diethyl monochloride and lactic acid rare earth compounding rare earth elements is 2:1, the mol ratio of divinyl and lactic acid rare earth compounding rare earth elements is 5:1, add 1.65ml hexane, the concentration that makes solution rare earth elements is 2 × 10
-5mol/ml, at 60 DEG C, ageing 1 hour, obtains rare earth catalyst.
Under the condition of nitrogen protection, be 10g/100ml divinyl hexane solution to adding 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free, then add rare earth catalyst, the mole number of rare earth catalyst rare earth elements and the mass ratio of divinyl are 4 × 10
-6mol/g, in 50 DEG C of reaction 1h, then with condensing polymkeric substance containing the ethanol of massfraction 1% antioxidant 264, after washing is pushed, 40 DEG C of vacuum-dryings, to constant weight, obtain polyhutadiene.
The polyhutadiene obtaining is analyzed, obtained experimental result in table 4.
Raw materials used and experimental result in table 4 embodiment 27～30
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a lactic acid rare earth compounding, is characterized in that, as shown in the formula (I):
Ln（C
3H
5O
3）
3·xL （I）；
Wherein, Ln is rare earth element; L is to electronics part; 0 < x≤4.
2. lactic acid rare earth compounding according to claim 1, is characterized in that, described L is alcohol compound, sulfoxide compound, aminated compounds or ester compound.
3. lactic acid rare earth compounding according to claim 2, is characterized in that, described alcohol compound is Virahol, isooctyl alcohol, hexalin or phenylcarbinol; Described sulfoxide compound is dimethyl sulfoxide (DMSO) or diphenyl sulfoxide.
4. lactic acid rare earth compounding according to claim 2, is characterized in that, described aminated compounds is diethylamine, triethylamine, n-Butyl Amine 99 or DMF.
5. lactic acid rare earth compounding according to claim 2, is characterized in that, described ester compound is TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
6. a preparation method for lactic acid rare earth compounding, is characterized in that, comprises the following steps:
Lactic acid rare earth compound is mixed in the first organic solvent with giving electronics part, and back flow reaction is carried out in heating, removes after the first organic solvent, obtains lactic acid rare earth compounding.
7. a preparation method for rare earth catalyst, is characterized in that, comprising:
Under the condition of protection of inert gas; lactic acid rare earth compounding described in claim 1～5 any one or prepared lactic acid rare earth compounding, aluminum alkyls, the first diolefin, the alkyl aluminum chloride of claim 6 are mixed with the second organic solvent; ageing, obtains rare earth catalyst.
8. preparation method according to claim 7, is characterized in that, the rare earth element in described lactic acid rare earth compounding and the mol ratio of aluminum alkyls are 1:(10～60); Rare earth element in described lactic acid rare earth compounding and the mol ratio of alkyl aluminum chloride are 1:(1～4).
9. preparation method according to claim 7, is characterized in that, the rare earth element in described lactic acid rare earth compounding and the mol ratio of the first diolefin are 1:(5～20).
10. an application for the prepared rare earth catalyst of claim 7～9 any one, is characterized in that, comprising:
The second diolefin, the second organic solvent are mixed with rare earth catalyst, react, obtain diolefin multipolymer.
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| CN114058076A (en) * | 2021-12-28 | 2022-02-18 | 湖南工业大学 | Rare earth nucleating agent, preparation method and application thereof, high-crystallinity modified polylactic acid film, and preparation method and application thereof |
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