CN103864827A - Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst - Google Patents
Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst Download PDFInfo
- Publication number
- CN103864827A CN103864827A CN201410122994.4A CN201410122994A CN103864827A CN 103864827 A CN103864827 A CN 103864827A CN 201410122994 A CN201410122994 A CN 201410122994A CN 103864827 A CN103864827 A CN 103864827A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- citric acid
- earth compounding
- acid rare
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a citric acid and rare earth complex, a rare earth catalyst as well as a preparation method and an application of the rare earth catalyst. The preparation method of the rare earth catalyst comprises the following steps: mixing citric acid and rare earth complex, alkyl aluminum, first diolefins, alkyl aluminum chloride and a second organic solvent under the condition of inert gas protection and aging so as to obtain the rare earth catalyst. Compared with the existing diolefin catalyst, the preparation method of the rare earth catalyst is simple, avoids dehydration and has no steep demand to the reaction condition; meanwhile, citric acid is a reagent commonly used in chemical industry, so that the rare earth catalyst 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 citric acid rare earth compounding, rare earth catalyst and preparation method thereof and application.
Background technology
Citric acid is the first acid in organic acid, is distributed widely in vegitabilia, as in lemon, gooseberry, raspberry, Sucus Vitis viniferae etc., can from plant material, extract, and also can carry out citric acid fermentation by sugar and make.Citric acid, at food with medically as sequestering agent, is also chemical intermediate, for the manufacture of carbonated drink, candy etc., also can be used as metal detergent, mordant etc.
Along with developing rapidly of rare-earth industry, the Application Areas of rare earth is also more and more wider, and the report of the synthetic aspect of relevant rare earth compound also increases thereupon, and these researchs have promoted the development of rare earth coordination chemistry.Wherein, the compound that citric acid and rare earth form, there is enhancing development, strengthen resistance against diseases, improve the effect of production level and reduction feed intake, be a kind of " supper vitamin " (Tian Junhua. the application [J] of citric acid rare-earth forage additive. feed review, 1999, 9 (3): 42-43.), be widely used in pig, chicken, fish, shrimp, ox, the raisings of the various animals such as sheep and special cultivation (Zhang Aimin. the short long agent of the compound rare-earth pork pig effect [J] of feeding. fodder industry, 1997, 18 (3): Liu 38-99. is gloomy greatly, Dan Anshan. the metabolism of rare-earth forage additive and security. fodder industry, 2001, 22 (11): 17-19), there are significant economic benefit and social benefit.
The compound that citric acid and rare earth form also can be used as the processing that thermo-stabilizer is widely used in the soft or hard goods such as PVC profiled material, tubing, sheet material, leatheroid, transparent article, be applicable to extruding, the complete processing such as injection moulding, calendering, blowing, in goods processing, there is low amount, efficient, good processability, photo and thermal stability and weathering resistance good, have coupling, solubilising, toughness reinforcing effect concurrently, meet the demand for development of environmentally friendly additives for plastics completely.
But the title complex of citric acid and rare earth formation is applied to diolefin polymerization as catalyzer and yet there are no report, the present invention considers to prepare the polyreaction of citric 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 citric acid rare earth compounding, rare earth catalyst and preparation method thereof and application, and this citric acid rare earth compounding can be used for the polyreaction of catalysis diolefin.
The invention provides a kind of citric acid rare earth compounding, as shown in the formula (I):
LnC
6H
5O
7·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 present invention also provides a kind of preparation method of citric acid rare earth compounding, comprises the following steps:
Citric 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 citric 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, citric 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 citric acid rare earth compounding and aluminum alkyls is 1:(10～60); Rare earth element in described citric 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 citric acid rare earth compounding and the first diolefin is 1:(5～20).
The present invention also provides a kind of application of weighing 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 citric 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; citric 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, citric 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):
LnC
6H
5O
7·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.
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 citric acid rare earth compounding, comprises the following steps:
Citric 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 citric 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 citric acid rare earth compound is preferably prepared in accordance with the following methods: the alcohol solution of citric acid is mixed with the alcohol solution of rare earth chloride, obtain mixing solutions, the pH value that regulates mixing solutions is alkalescence, filters, and obtains citric acid rare earth compound.
The present invention mixes the alcohol solution of citric acid with the alcohol solution of rare earth chloride, obtain mixing solutions.Wherein, described alcohol solution is alcohol solution well known to those skilled in the art, there is no special restriction, and the volume that is preferably alcohol and water in the present invention is (1～2): the alcohol solution of (2～1); Described alcohol solution is preferably methanol aqueous solution and/or aqueous ethanolic solution, more preferably aqueous ethanolic solution; Described rare earth chloride is preferably Lanthanum trichloride, Neodymium trichloride, samarium trichloride, Erbium trichloride or Ytterbium trichloride; The temperature of described mixing is preferably 40 DEG C～60 DEG C.
According to the present invention, the method for described mixing preferably slowly splashes into the alcohol solution of rare earth chloride in the alcohol solution of citric acid, mixes.
The pH value that regulates mixing solutions is alkalescence, and the present invention preferably adopts alkali metal hydroxide to regulate the pH value of mixing solutions, and more preferably adopting sodium hydroxide and/or potassium hydroxide to regulate the pH value of mixing solutions is alkalescence; It is 4～5 that the present invention preferably regulates the pH value of mixing solutions.
After the ph value of adjusting mixing solutions is alkalescence, precipitated in a large number, filtered, after preferably filtering, washed 2～3 times with alcohol, more preferably used absolute ethanol washing 2～3 times, dry, obtain citric acid rare earth compound.
Described citric 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 citric 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 citric acid rare earth compounding.
The present invention also provides and has adopted above-mentioned citric acid rare earth compounding to prepare the method for rare earth catalyst; comprise: under the condition of protection of inert gas; citric 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, citric 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 citric 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 citric 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 citric 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 citric 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, citric 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, citric 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 are dissolved in citric acid and Neodymium trichloride respectively in the aqueous ethanolic solution that volume ratio is 1:1, be at 50 DEG C in temperature, after Neodymium trichloride aqueous ethanolic solution is slowly splashed in citric acid aqueous ethanolic solution, be 4～5 in mixed solution and dripping sodium hydroxide solution to pH value, precipitated in a large number, filter, use absolute ethanol washing 2～3 times, the dry citric acid neodymium compound that obtains.
1.2 is 1:3 by the citric acid neodymium compound obtaining in 1.1 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 citric acid rare earth compounding NdC
6h
5o
73 (CH
3)
2c (CH
2)
5oH.
Embodiment 2
The ratio that is 1:2 according to mol ratio by the citric acid neodymium compound obtaining in 1.1 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 citric acid rare earth compounding Nd C
6h
5o
72CH
3cH
2nH
2.
Embodiment 3
The ratio that is 1:3 according to mol ratio by the citric acid neodymium compound obtaining in 1.1 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 citric acid rare earth compounding NdC
6h
5o
73TBP.
Embodiment 4
4.1 are dissolved in citric acid and Lanthanum trichloride respectively in the aqueous ethanolic solution that volume ratio is 1:1, be at 50 DEG C in temperature, after Lanthanum trichloride aqueous ethanolic solution is slowly splashed in citric acid aqueous ethanolic solution, be 4～5 in mixed solution and dripping sodium hydroxide solution to pH value, precipitated in a large number, filter, use absolute ethanol washing 2～3 times, the dry citric acid lanthanum compound that obtains.
4.2 is 1:2 by the citric acid lanthanum compound obtaining in 4.1 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 citric acid rare earth compounding LaC
6h
5o
72
Embodiment 5
The ratio that is 1:3 according to mol ratio by the citric acid lanthanum compound obtaining in 4.1 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 citric acid rare earth compounding
Embodiment 6
The ratio that is 1:3 according to mol ratio by the citric acid lanthanum compound obtaining in 4.1 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 citric acid rare earth compounding La C
6h
5o
73 (CH
3cH
2)
2nH.
Embodiment 7
The ratio that is 1:3 according to mol ratio by the citric acid lanthanum compound obtaining in 4.1 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 citric acid rare earth compounding LaC
6h
5o
73TPP.
Embodiment 8
8.1 are dissolved in citric acid and samarium trichloride respectively in the aqueous ethanolic solution that volume ratio is 1:1, be at 50 DEG C in temperature, after samarium trichloride aqueous ethanolic solution is slowly splashed in citric acid aqueous ethanolic solution, be 4～5 in mixed solution and dripping sodium hydroxide solution to pH value, precipitated in a large number, filter, use absolute ethanol washing 2～3 times, the dry citric acid samarium compound that obtains.
8.2 is 1:2 by the citric acid samarium compound obtaining in 8.1 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 citric acid rare earth compounding Sm C
6h
5o
72 (CH
3cH
2)
3n.
Embodiment 9
The ratio that is 1:2 according to mol ratio by the citric acid samarium compound obtaining in 8.1 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 citric acid rare earth compounding SmC
6h
5o
72DBP.
Embodiment 10
10.1 are dissolved in citric acid and Erbium trichloride respectively in the aqueous ethanolic solution that volume ratio is 1:1, be at 50 DEG C in temperature, after Erbium trichloride aqueous ethanolic solution is slowly splashed in citric acid aqueous ethanolic solution, be 4～5 in mixed solution and dripping sodium hydroxide solution to pH value, precipitated in a large number, filter, use absolute ethanol washing 2～3 times, the dry citric acid erbium compound that obtains.
10.2 is 1:3 by the citric acid erbium compound obtaining in 10.1 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 citric acid rare earth compounding ErC
6h
5o
73 (CH
3)
2cHOH.
Embodiment 11
By the citric acid erbium compound and the N that obtain in 10.1, the ratio that dinethylformamide is 1:4 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 citric acid rare earth compounding ErC
6h
5o
74C
3h
7nO.
Embodiment 12
12.1 are dissolved in citric acid and Ytterbium trichloride respectively in the aqueous ethanolic solution that volume ratio is 1:1, be at 50 DEG C in temperature, after Ytterbium trichloride aqueous ethanolic solution is slowly splashed in citric acid aqueous ethanolic solution, be 4～5 in mixed solution and dripping sodium hydroxide solution to pH value, precipitated in a large number, filter, use absolute ethanol washing 2～3 times, the dry citric acid ytterbium compound that obtains.
12.2 is 1:3 by the citric acid ytterbium compound obtaining in 12.1 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 citric acid rare earth compounding YbC
6h
5o
73
Embodiment 13
The ratio that is 1:3 according to mol ratio by the citric acid ytterbium compound obtaining in 12.1 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 citric acid rare earth compounding
Embodiment 14
The ratio that is 1:3 according to mol ratio by the citric acid ytterbium compound obtaining in 12.1 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
6h
5o
73CH
3(CH
2)
2nH
2.
Embodiment 15
The ratio that is 1:3 according to mol ratio by the citric acid ytterbium compound obtaining in 12.1 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 citric acid rare earth compounding YbC
6h
5o
73DOP.
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 citric 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 citric acid rare earth compounding is in table 1, the mol ratio of triethyl aluminum and citric acid rare earth compounding rare earth elements is 10:1, the mol ratio of diisobutyl aluminum chloride and citric acid rare earth compounding rare earth elements is 2:1, the mol ratio of isoprene and citric 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 citric 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 citric acid rare earth compounding is in table 2, the mol ratio of triisobutyl aluminium and citric acid rare earth compounding rare earth elements is 20:1, the mol ratio of aluminium diethyl monochloride and citric acid rare earth compounding rare earth elements is 3:1, the mol ratio of isoprene and citric 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 citric 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 citric acid rare earth compounding is in table 3, the mol ratio of ADEH and citric acid rare earth compounding rare earth elements is 40:1, the mol ratio of aluminium diethyl monochloride and citric acid rare earth compounding rare earth elements is 1:1, the mol ratio of isoprene and citric 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 citric 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 citric acid rare earth compounding is in table 4, the mol ratio of diisobutylaluminium hydride and citric acid rare earth compounding rare earth elements is 60:1, the mol ratio of aluminium diethyl monochloride and citric acid rare earth compounding rare earth elements is 2:1, the mol ratio of divinyl and citric 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 27～20
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 citric acid rare earth compounding, is characterized in that, as shown in the formula (I):
LnC
6H
5O
7·xL （I）；
Wherein, Ln is rare earth element; L is to electronics part; 0 < x≤4.
2. citric 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. citric 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. citric 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. citric 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 citric acid rare earth compounding, is characterized in that, comprises the following steps:
Citric 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 citric 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; citric acid rare earth compounding described in claim 1～5 any one or prepared citric 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 citric acid rare earth compounding and the mol ratio of aluminum alkyls are 1:(10～60); Rare earth element in described citric 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 citric 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410122994.4A CN103864827B (en) | 2014-03-28 | 2014-03-28 | Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410122994.4A CN103864827B (en) | 2014-03-28 | 2014-03-28 | Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103864827A true CN103864827A (en) | 2014-06-18 |
| CN103864827B CN103864827B (en) | 2017-01-18 |
Family
ID=50903894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410122994.4A Active CN103864827B (en) | 2014-03-28 | 2014-03-28 | Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103864827B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201222A (en) * | 2017-05-03 | 2017-09-26 | 河南大学 | A kind of two-dimentional rare earth coordination polymer fluorescent material and preparation method thereof |
| CN110144025A (en) * | 2019-05-20 | 2019-08-20 | 中国科学院长春应用化学研究所 | A kind of preparation method of rare earth catalyst and its application in diolefin polymerization and combined polymerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220655A (en) * | 1997-03-05 | 1999-06-23 | 罗狄亚化学公司 | Preparation of solid powdery rare earth carboxylates by evaporation method |
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN101824114A (en) * | 2009-12-24 | 2010-09-08 | 中国科学院长春应用化学研究所 | Sulfoacid rare earth catalyst for polymerizing high-cis-isoprene rubber and preparation method thereof |
-
2014
- 2014-03-28 CN CN201410122994.4A patent/CN103864827B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220655A (en) * | 1997-03-05 | 1999-06-23 | 罗狄亚化学公司 | Preparation of solid powdery rare earth carboxylates by evaporation method |
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN101824114A (en) * | 2009-12-24 | 2010-09-08 | 中国科学院长春应用化学研究所 | Sulfoacid rare earth catalyst for polymerizing high-cis-isoprene rubber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董丽丹: "稀土掺杂有机配合物的合成与性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201222A (en) * | 2017-05-03 | 2017-09-26 | 河南大学 | A kind of two-dimentional rare earth coordination polymer fluorescent material and preparation method thereof |
| CN110144025A (en) * | 2019-05-20 | 2019-08-20 | 中国科学院长春应用化学研究所 | A kind of preparation method of rare earth catalyst and its application in diolefin polymerization and combined polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103864827B (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104447274B (en) | The recoverying and utilizing method of long carbochain biatomic acid purification crystalline mother solution | |
| CN101812207B (en) | Preparation method of PVC (Polyvinyl Chloride) phenol-free heat stabilizer | |
| CN109232178B (en) | Novel method for preparing high-purity hydroxytyrosol | |
| CN103736384A (en) | Treatment process of glyphosate hydrolyzing tail gas | |
| CN104447280B (en) | The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution | |
| CN103420918A (en) | Simple and convenient preparation method of key intermediate (2-methyl-4-amino-5-amino methyl pyrimidine) for vitamin B1 | |
| CN103864827A (en) | Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst | |
| CN104529747A (en) | Purification method of dodecanedioic acid | |
| CN102766050A (en) | Method for synthesizing dimethyl fumarate | |
| CN109053389B (en) | Synthetic method of 2,4, 6-tribromophenyl allyl ether | |
| CN104370956A (en) | Efficient synthesis method of antioxidant 168 | |
| US20120130074A1 (en) | Method for Preparation Metal Compounds of 8-Hydroxyquinoline or Derivatives | |
| CN108863886A (en) | It is a kind of to prepare 3-（3- chloropropyl）The method of -4- oxo-pyrrolidine -1- carboxylic acid, ethyl ester | |
| CN104326989B (en) | The preparation method of 2-methyl-4-amino-5-(amino methyl) pyrimidine | |
| CN110305006A (en) | The processing method of long carbochain biatomic acid purification waste liquid | |
| CN101759553A (en) | Method for preparing alpha-calcium picrolonate | |
| CN109721549B (en) | Urea pyrimidine Schiff base and preparation method and application thereof | |
| CN104151736A (en) | Preparation method of composite lanthanum carboxylate thermal stabilizer for PVC (polyvinyl chloride) | |
| CN104529726A (en) | Preparation method of hydroxyacetophenone | |
| CN103694599A (en) | Efficient and environment-friendly polyvinyl chloride heat stabilizer and preparation method thereof | |
| CN102702387A (en) | Preparation method and using method for sterilization type sludge dehydrant | |
| CN106365987A (en) | Synthesis method of paraben compounds marked by stable isotope 13C or D | |
| CN102382071B (en) | Technology for preparing 1H-tetrazoleacetic acid with deamination reduction method | |
| CN103159612B (en) | Industrialization production technology for extracting ginkgolic acid from Ginkgo testa | |
| CN101775029A (en) | Convenient synthesis method for alkyl substitution phenyloboricacid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |