CN103626890A - Rare earth catalytic system and preparation method thereof as well as preparation method of butadiene-isoprene - Google Patents
Rare earth catalytic system and preparation method thereof as well as preparation method of butadiene-isoprene Download PDFInfo
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- CN103626890A CN103626890A CN201310615616.5A CN201310615616A CN103626890A CN 103626890 A CN103626890 A CN 103626890A CN 201310615616 A CN201310615616 A CN 201310615616A CN 103626890 A CN103626890 A CN 103626890A
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Abstract
The invention provides a rare earth catalytic system, comprises a rare earth oxide complex and an aluminum alkyl compound; the chemical composition of the rare earth oxide complex is Ln2O3.xR.yL, wherein Ln is a rare earth element, R is an acid compound, L is a compound with a donor ligand, x is more than 0 and not more than 4, y is not less than 0 and not more than 3. Compared with the prior art, the step of preparing the rare earth oxide into rear earth carboxylate is unnecessary, chloride does not need to be added as a catalyst, and the step of preparing the rare earth oxide into a rare earth chloride as a catalyst through a complicated process is also unnecessary. The rare earth catalytic system provided by the invention is simple in preparation process and convenient to operate, and the demand on the reaction condition is low. Furthermore, the rare earth catalytic system provided by the invention does not contain chlorine element so that the production equipment cannot be corroded by the chlorine element.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to the preparation method of a kind of rare-earth catalysis system and preparation method thereof and butadiene isoprene copolymer.
Background technology
Divinyl and isoprene are carried out to copolymerization with coordination catalyst, existing a lot of reports, transition metal used mostly is the elements such as Ti, Co, Ni.This class catalyzer is different to the orienting effect of divinyl and isoprene homopolymerization, the performance of the copolymerization glue therefore making by these systems is undesirable, and rare-earth catalysis system is the excellent catalysts of conjugated diolefin tactic polymerization, same rare earth catalyst just can make divinyl, isoprene all aggregate into the polymkeric substance of high-cis, this multipolymer has not only been taken into account the premium properties of (IR) of cis-1,4-polybutadiene rubber (BR) and polyisoprene rubber, also have very strong cold tolerance, any rubber phase that its excellent cold resistant property almost can be known with us matches in excellence or beauty simultaneously.Therefore, adopting rare-earth catalysis system to prepare butadiene isoprene copolymer is subject to the people's attention.
Publication number is that Chinese patent and the US Patent No. 7022783B2 of CN101831032A reported the synthetic butadiene isoprene copolymer of the ternary RE catalyst system that adopts rare earth compound, aluminum alkyls and muriate to form; Publication number is that the Chinese patent of CN1296982A adopts ternary RE system, and the mode of aluminum mixture has been prepared the controlled butadiene isoprene copolymer of molecular weight; Publication number is that the Chinese patent of CN1295087A is with rare earth chloride binary system polymerization divinyl and isoprene.But the disclosed rare-earth catalysis system of prior art need to be prepared into rare earth oxide rare earth carboxylate and add muriate as the 3rd component, or rare earth oxide is made to rare earth chloride and just there is activity, the complicated process of preparation of this rare earth carboxylate or rare earth chloride, complex operation, the technical parameters such as the pressure of reaction, temperature, time are required to harshness, time-consuming, be unfavorable for the widespread use of rare-earth catalysis system.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of rare-earth catalysis system, the preparation process of this rare-earth catalysis system is simple, easy and simple to handle, lower to reaction conditions requirement, has good application prospect.
The invention provides a kind of rare-earth catalysis system, comprise rare earth oxide title complex and alkylaluminium cpd;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
Preferably, described Ln comprises a kind of in lanthanum, neodymium, samarium, erbium and ytterbium.
Preferably, described R comprises a kind of in carboxylic acid, hydrochloric acid and sulfonic acid.
Preferably, described L comprises a kind of in alcohol compound, sulfoxide compound, nitrogenous compound and ester compound.
Preferably, described alkylaluminium cpd comprises a kind of in trialkylaluminium and alkyl-al hydride.
Preferably, the mol ratio of described rare earth oxide title complex rare earth elements and alkylaluminium cpd is 1:(20～60).
Preferably, the volumetric molar concentration of described rare-earth catalysis system rare earth elements is 2 * 10
-5mol/mL～5 * 10
-5mol/mL.
Preferably, the preparation method of described rare earth oxide title complex comprises the following steps:
By rare earth oxide, acidic cpd with give electronics ligand compound mixed grinding, the rare earth oxide title complex of the chemical constitution shown in (I) that obtains thering is formula.
Preferably, the time of described grinding is 30 hours～200 hours.
The preparation method who the invention provides a kind of rare-earth catalysis system, comprises the following steps:
Rare earth oxide title complex and alkylaluminium cpd are mixed, the mixed system obtaining is carried out to ripening, obtain rare-earth catalysis system;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
Preferably, the temperature of described ripening is 20 ℃～80 ℃;
The time of described ripening is 1 hour～24 hours.
The preparation method who the invention provides a kind of butadiene isoprene copolymer, comprises the following steps:
Under the effect of catalyzer, under the condition of anhydrous and oxygen-free, divinylic monomer and isoprene monomer are carried out to polyreaction in organic solvent, obtain butadiene isoprene copolymer;
Described catalyzer is rare-earth catalysis system prepared by rare-earth catalysis system described in technique scheme or the method described in technique scheme.
Preferably, the ratio of the mole number of described Rare Earths in Catalyst element and divinylic monomer and isoprene monomer total mass is 1.0 * 10
-6mol/g～8.0 * 10
-6mol/g.
Preferably, the temperature of described polyreaction is 20 ℃～80 ℃;
The time of described polyreaction is 1 hour～24 hours.
The invention provides a kind of rare-earth catalysis system, comprise rare earth oxide title complex and alkylaluminium cpd; Described rare earth oxide title complex has the chemical constitution shown in formula (I); Wherein, Ln is rare earth element; R is acidic cpd; L is to electronics ligand compound; 0 < x≤4; 0≤y≤3.Compared with prior art, the present invention uses as catalyzer without rare earth oxide being prepared into rare earth carboxylate and not needing to add muriate, also without rare earth oxide is made to rare earth chloride by complicated technique, as catalyzer, uses.The preparation process of rare-earth catalysis system provided by the invention is simple, easy and simple to handle, lower to the requirement of reaction conditions.In addition not chloride element in rare-earth catalysis system provided by the invention, the corrosion that can avoid chlorine element to bring to production unit.
Experimental result shows, in the butadiene unit of the butadiene isoprene copolymer that rare-earth catalysis system provided by the invention prepares cis-1,4 structural contents are up to 98.4%, in the isoprene unit of butadiene isoprene copolymer cis-1,4 structural contents are up to 98.7%, and the polymerization yield of butadiene isoprene copolymer is up to 70.7%.
Embodiment
The invention provides a kind of rare-earth catalysis system, comprise rare earth oxide title complex and alkylaluminium cpd;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
Compared with prior art, the present invention uses as catalyzer without rare earth oxide being prepared into rare earth carboxylate and not needing to add muriate, also without rare earth oxide is made to rare earth chloride by complicated technique, as catalyzer, uses.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, lower to the requirement of reaction conditions.
Rare-earth catalysis system provided by the invention comprises rare earth oxide title complex, and described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element, is preferably a kind of in lanthanum, neodymium, samarium, erbium and ytterbium;
R is acidic cpd, is preferably a kind of in carboxylic acid, hydrochloric acid (HCl) and sulfonic acid, more preferably formic acid (HCOOH), HCl and trifluoromethanesulfonic acid (HCF
3sO
3) in a kind of;
L is to electronics ligand compound, is preferably a kind of in alcohol compound, sulfoxide compound, nitrogenous compound and lipoid substance, more preferably Virahol ((CH
3)
2cHOH), isooctyl alcohol ((CH
3)
2c (CH
2)
5oH), hexalin, phenylcarbinol, dimethyl sulfoxide (DMSO), diphenyl sulfoxide, pyridine (Py), second bipyridine (DPy), phenanthroline (Phen), DMF (C
3h
7nO), a kind of in TRI N BUTYL PHOSPHATE (TBP), triphenylphosphate (TPP), diisobutyl phthalate (DBP) and o-phthalic acid dibutyl ester (DOP); Most preferably be (CH
3)
2cHOH, (CH
3)
2c (CH
2)
5oH, hexalin, dimethyl sulfoxide (DMSO), diphenyl sulfoxide, Py, DPy, Phen, C
3h
7a kind of in NO, TBP, TPP, DBP and DOP;
0 < x≤4, preferred, 1≤x≤4; Preferred, 1≤x≤3;
0≤y≤3, preferred, 1≤y≤2.
In the present invention, described rare earth oxide title complex preferably prepares by the following method:
By rare earth oxide, acidic cpd with give electronics ligand compound mixed grinding, the rare earth oxide title complex of the chemical constitution shown in (I) that obtains thering is formula.
In the present invention, described rare earth oxide, acidic cpd and be preferably 1:x:y to the mol ratio of electronics ligand compound, 0 < x≤4, preferred, 1≤x≤4, preferred, 1≤x≤3; 0≤y≤3, preferred, 1≤y≤2.In the present invention, described rare earth oxide has the molecular formula shown in formula (II):
Ln
2O
3（II），
Ln in formula (II) is consistent with Ln described in technique scheme, does not repeat them here; In the present invention, described acidic cpd and the kind and acidic cpd described in technique scheme and consistent to the kind of electronics ligand compound of giving electronics ligand compound, do not repeat them here.The present invention is to described rare earth oxide, acidic cpd and there is no special restriction to the source of electronics ligand compound, adopt the rare earth oxide, acidic cpd of mentioned kind well known to those skilled in the art and to electronics ligand compound, as bought acquisition by market.The present invention does not have special restriction to the method for described mixing and grinding, adopts the technical scheme of mixing well known to those skilled in the art and grinding; The present invention, preferably by rare earth oxide, acidic cpd with mix to electronics ligand compound in mill, grinds, the rare earth oxide title complex of the chemical constitution shown in (I) that obtains having formula; In the present invention, the time of described grinding is preferably 30 hours～and 200 hours, more preferably 60 hours～160 hours, most preferably be 100 hours～120 hours.
Prepare after rare earth oxide title complex, the present invention carries out ultimate analysis test to it, and test result shows that the chemical constitution of rare earth oxide title complex prepared by the present invention is Ln
2o
3xRyL, wherein Ln, R, L, x and y are consistent with Ln, R, L, x and y described in technique scheme.
Rare-earth catalysis system provided by the invention comprises alkylaluminium cpd, and described alkylaluminium cpd is preferably a kind of in trialkylaluminium and alkyl-al hydride, more preferably diisobutylaluminium hydride (Al (i-Bu)
2h), ADEH (AlEt
2h), triisobutyl aluminium (Al (i-Bu)
3), triethyl aluminum (AlEt
3) and octyl group aluminium (Al (C
8h
17)
3) in a kind of.The present invention does not have special restriction to the source of described alkylaluminium cpd, adopts the alkylaluminium cpd of mentioned kind well known to those skilled in the art, as bought and be obtained by market.
In order to reduce the concentration of rare-earth catalysis system provided by the invention, weaken the fierce degree of rare earth oxide title complex and aluminum alkyls reaction, in the present invention, described rare-earth catalysis system preferably also comprises organic solvent.The present invention does not have special restriction to the kind of described organic solvent, adopts organic solvent well known to those skilled in the art; In the present invention, described organic solvent is preferably alkane or aromatic hydrocarbon, and the alkane that more preferably C atomicity is 5～8, most preferably is hexane; Rare-earth catalysis system that the present invention adopts hexane to prepare as solvent is nontoxic, environmental protection.The present invention does not have special restriction to the source of described organic solvent, adopts the organic solvent of mentioned kind well known to those skilled in the art, as bought and be obtained by market.In the present invention, the quality of described organic solvent makes the volumetric molar concentration of rare-earth catalysis system rare earth elements preferably reach 2 * 10
-5mol/mL～5 * 10
-5mol/mL, more preferably reaches 3 * 10
-5mol/mL～4 * 10
-5mol/mL.
In the present invention, the rare earth element in described rare earth oxide title complex and the mol ratio of alkylaluminium cpd are preferably 1:(20～60), 1:(30～50 more preferably), most preferably be 1:(35～45).
The preparation method who the invention provides a kind of rare-earth catalysis system, comprises the following steps:
Rare earth oxide title complex and alkylaluminium cpd are mixed, the mixed system obtaining is carried out to ripening, obtain rare-earth catalysis system;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
The present invention preferably joins rare earth oxide title complex, alkylaluminium cpd in reaction vessel and mixes successively, then the mixed system obtaining is carried out to ripening, obtains rare-earth catalysis system.In the present invention, described mixed system preferably also comprises organic solvent; The present invention preferably joins rare earth oxide title complex, alkylaluminium cpd and organic solvent in reaction vessel and mixes successively, then the mixed system obtaining is carried out to ripening, obtains rare-earth catalysis system.The present invention does not have special restriction to the method for described mixing, adopts the technical scheme of mixing well known to those skilled in the art.The present invention preferably mixes under the protection of nitrogen.In the present invention, the consumption of described organic solvent makes the volumetric molar concentration of the rare-earth catalysis system rare earth elements for preparing be preferably 2 * 10
-5mol/mL～5 * 10
-5mol/mL, more preferably 3 * 10
-5mol/mL～4 * 10
-5mol/mL.
In the present invention, the kind of described rare earth oxide title complex, alkylaluminium cpd and organic solvent is consistent with kind and the source of rare earth oxide title complex, alkylaluminium cpd and organic solvent described in technique scheme with source, does not repeat them here.In the present invention, the ratio of the mole number of the mole number of described alkylaluminium cpd and rare earth oxide title complex rare earth elements is preferably (20～60): 1, more preferably (30～50): 1, most preferably be (35～45): 1.
Obtain after the mixed system of rare earth oxide title complex and alkylaluminium cpd, the present invention carries out ripening by described mixed system, obtains rare-earth catalysis system.In the present invention, the temperature of described ripening is preferably 20 ℃～80 ℃, more preferably 35 ℃～65 ℃, most preferably is 45 ℃～55 ℃; The time of described ripening is preferably 1 hour～and 24 hours, more preferably 6 hours～18 hours, most preferably be 10 hours～15 hours.
The preparation method who the invention provides a kind of butadiene isoprene copolymer, comprises the following steps:
Under the effect of catalyzer, under the condition of anhydrous and oxygen-free, divinylic monomer and isoprene monomer are carried out to polyreaction in organic solvent, obtain butadiene isoprene copolymer;
Described catalyzer is rare-earth catalysis system prepared by rare-earth catalysis system described in technique scheme or the method described in technique scheme.
The present invention preferably joins divinylic monomer and isoprene monomer in organic solvent, obtain butadiene-isoprene solution, under the effect of catalyzer, under the condition of anhydrous and oxygen-free, butadiene-isoprene solution is carried out to polyreaction, obtain butadiene isoprene copolymer; More preferably under the condition of anhydrous and oxygen-free, catalyzer is joined in above-mentioned butadiene-isoprene solution and carries out polyreaction, obtain butadiene isoprene copolymer; Most preferably under the protection of nitrogen, and under the condition of anhydrous and anaerobic, after adding above-mentioned butadiene-isoprene solution in reaction vessel, add again catalyzer, carry out polyreaction, obtain butadiene isoprene copolymer.
In the present invention, the mass ratio of described divinylic monomer and isoprene monomer is preferably (90～10): (10～90), more preferably (80～20): (20～80), most preferably are (70～30): (30～70), are the most preferably (45～55): (55～45).In the present invention, described catalyzer is rare-earth catalysis system prepared by rare-earth catalysis system described in technique scheme or the method described in technique scheme.The present invention does not have special restriction to the kind of described organic solvent, adopts the butadiene isoprene copolymer organic solvent used of preparing well known to those skilled in the art; In the present invention, described organic solvent can be identical with the organic solvent described in technique scheme, also can be different from the organic solvent described in technique scheme.In the present invention, described organic solvent is preferably alkane or aromatic hydrocarbon, and the alkane that more preferably C atomicity is 5～8, most preferably is hexane; The present invention adopts hexane as the solvent in above-mentioned polyreaction, and the process of preparing butadiene isoprene copolymer is nontoxic, environmental protection; The present invention does not have special restriction to the source of described organic solvent, adopts the organic solvent of mentioned kind well known to those skilled in the art, as bought and be obtained by market.In the present invention, the consumption of described organic solvent makes the mass concentration of butadiene-isoprene solution be preferably 8g/100mL～12g/100mL, and more preferably 9g/100mL～11g/100mL, most preferably is 10g/100mL.
In the present invention, the consumption of described catalyzer makes the mole number of rare-earth catalysis system rare earth elements and the ratio of divinylic monomer and isoprene monomer total mass be preferably 1.0 * 10
-6mol/g～8.0 * 10
-6mol/g, more preferably 2.0 * 10
-6mol/g～6.0 * 10
-6mol/g, most preferably is 3.0 * 10
-6mol/g～5.0 * 10
-6mol/g.
In the present invention, the temperature of described polyreaction is preferably 20 ℃～80 ℃, more preferably 35 ℃～65 ℃, most preferably is 45 ℃～55 ℃; The time of described polyreaction is preferably 1 hour～and 24 hours, more preferably 4 hours～20 hours, most preferably be 8 hours～16 hours, be the most preferably 10 hours～14 hours.
Complete after described polyreaction the ethanolic soln termination reaction of the BHT that the present invention is preferably 1% with massfraction, polymkeric substance settles out in ethanol, after washing with alcohol extruding, vacuum-drying, to constant weight, obtains butadiene isoprene copolymer.
The present invention carries out structure determination by the butadiene isoprene copolymer preparing by infrared spectra.Detected result shows, adopts the cis-Isosorbide-5-Nitrae structural content of divinyl in the butadiene isoprene copolymer that rare-earth catalysis system provided by the invention prepares to be up to 98.4%, and the cis-Isosorbide-5-Nitrae structural content of isoprene is up to 98.7%.
The present invention has calculated the polymerization yield of the butadiene isoprene copolymer preparing, and the present invention does not have special restriction to the method for calculation of described polymerization yield, adopts the method for calculating polymerization yield well known to those skilled in the art.The calculation result of butadiene isoprene copolymer polymerization yield shows, adopts rare-earth catalysis system provided by the invention to prepare butadiene isoprene copolymer, and its polymerization yield reaches as high as 70.7%.
The invention provides a kind of rare-earth catalysis system, comprise rare earth oxide title complex and alkylaluminium cpd; Described rare earth oxide title complex has the chemical constitution shown in formula (I); Wherein, Ln is rare earth element; R is acidic cpd; L is to electronics ligand compound; 0 < x≤4; 0≤y≤3.Compared with prior art, the present invention uses as catalyzer without rare earth oxide being prepared into rare earth carboxylate and not needing to add muriate, also without rare earth oxide is made to rare earth chloride by complicated technique, as catalyzer, uses.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, lower to the requirement of reaction conditions.In addition not chloride element in rare-earth catalysis system provided by the invention, the corrosion that can avoid chlorine element to bring to production unit.
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
By Nd
2o
3and HCF
3sO
3the ratio that is 1:3 according to mol ratio joins in mill, grinds 30 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 1 is tested, and detected result is as shown in table 1, the chemical constitution of the rare earth oxide title complex that table 1 obtains for the embodiment of the present invention 1～embodiment 14.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
3hexane solution 3mL, then to the hexane that adds 2mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 3 * 10
-5the solution of mol/mL, by the solution obtaining ageing 15 hours at 50 ℃, obtains rare-earth catalysis system.
Embodiment 2
By La
2o
3, HCOOH and (CH
3)
2the ratio that CHOH is 1:4:3 according to mol ratio joins in mill, grinds 60 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 2 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
2h hexane solution 3mL, then to the hexane that adds 2mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 2 * 10
-5the solution of mol/mL, by the solution obtaining ageing 1 hour at 80 ℃, obtains rare-earth catalysis system.
Embodiment 3
By Sm
2o
3, HCF
3sO
3(CH
3)
2c (CH
2)
5the ratio that OH is 1:1:2 according to mol ratio joins in mill, grinds 90 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 3 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4al (the C of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
8h
17)
3hexane solution 1.5mL, then to the hexane that adds 0.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 5 hours at 70 ℃, obtains rare-earth catalysis system.
Embodiment 4
By Er
2o
3, HCl and hexalin be 1:3:3 according to mol ratio ratio joins in mill, grinds 120 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 4 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4the Al (i-Bu) of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
2h hexane solution 2mL, then to the hexane that adds 3mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 10 hours at 60 ℃, obtains rare-earth catalysis system.
Embodiment 5
By Nd
2o
3, HCl and dimethyl sulfoxide (DMSO) be 1:2:2 according to mol ratio ratio joins in mill, grinds 150 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 5 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the Al (i-Bu) of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
2h hexane solution 1.5mL, then to the hexane that adds 1.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 24 hours at 20 ℃, obtains rare-earth catalysis system.
Embodiment 6
By Yb
2o
3, HCF
3sO
3the ratio that is 1:2:3 according to mol ratio with diphenyl sulfoxide joins in mill, grinds 180 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 6 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4al (the C of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
8h
17)
3hexane solution 1.5mL, then to the hexane that adds 0.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 5 hours at 70 ℃, obtains rare-earth catalysis system.
Embodiment 7
By Nd
2o
3, HCF
3sO
3the ratio that is 1:2:3 according to mol ratio with Py joins in mill, grinds 200 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 7 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
3hexane solution 3mL, then to the hexane that adds 2mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 3 * 10
-5the solution of mol/mL, by the solution obtaining ageing 15 hours at 50 ℃, obtains rare-earth catalysis system.
Embodiment 8
By Yb
2o
3, HCF
3sO
3the ratio that is 1:3:3 according to mol ratio with DPy joins in mill, grinds 200 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 8 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the Al (i-Bu) of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
2h hexane solution 1.5mL, then to the hexane that adds 1.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 24 hours at 20 ℃, obtains rare-earth catalysis system.
Embodiment 9
By La
2o
3, HCl and Phen be 1:2:2 according to mol ratio ratio joins in mill, grinds 100 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 9 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
2h hexane solution 3mL, then to the hexane that adds 2.0mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 2 * 10
-5the solution of mol/mL, by the solution obtaining ageing 1 hour at 80 ℃, obtains rare-earth catalysis system.
Embodiment 10
By La
2o
3, HCl and C
3h
7the ratio that NO is 1:2:3 according to mol ratio joins in mill, grinds 80 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 10 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4al (the C of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
8h
17)
3hexane solution 1.5mL, then to the hexane that adds 0.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 5 hours at 70 ℃, obtains rare-earth catalysis system.
Embodiment 11
By Yb
2o
3, HCF
3sO
3the ratio that is 1:3:3 according to mol ratio with TBP joins in mill, grinds 60 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 11 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
3hexane solution 3mL, then to the hexane that adds 2mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 3 * 10
-5the solution of mol/mL, by the solution obtaining ageing 15 hours at 50 ℃, obtains rare-earth catalysis system.
Embodiment 12
By Nd
2o
3, HCF
3sO
3the ratio that is 1:2:2 according to mol ratio with TPP joins in mill, grinds 160 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 12 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4the Al (i-Bu) of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
2h hexane solution 2mL, then to the hexane that adds 3mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 10 hours at 60 ℃, obtains rare-earth catalysis system.
Embodiment 13
By La
2o
3, HCF
3sO
3the ratio that is 1:3:1 according to mol ratio with DBP joins in mill, grinds 120 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 13 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.5 * 10
-4the above-mentioned rare earth oxide title complex preparing of mol, the AlEt of 2.0mol/L
2h hexane solution 3mL, then to the hexane that adds 2.0mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 2 * 10
-5the solution of mol/mL, by the solution obtaining ageing 1 hour at 80 ℃, obtains rare-earth catalysis system.
Embodiment 14
By Yb
2o
3, HCOOH and DOP be 1:2:3 according to mol ratio ratio joins in mill, grinds 120 hours, obtains rare earth oxide title complex.
The rare earth oxide title complex that the present invention obtains embodiment 14 is tested, and detected result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, add successively 0.75 * 10
-4the Al (i-Bu) of the above-mentioned rare earth oxide title complex preparing of mol, 2.0mol/L
2h hexane solution 1.5mL, then to the hexane that adds 1.5mL in the mixing solutions obtaining, the volumetric molar concentration that obtains rare earth element is 5 * 10
-5the solution of mol/mL, by the solution obtaining ageing 24 hours at 20 ℃, obtains rare-earth catalysis system.
The chemical constitution of the rare earth oxide title complex that table 1 embodiment of the present invention 1～embodiment 14 obtains
Embodiment 15
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 90:10; the rare-earth catalysis system that adds again embodiment 5 to prepare; at 50 ℃, carry out polyreaction 24 hours, the mole number that the consumption of described rare-earth catalysis system meets Nd in rare-earth catalysis system is 5 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 15 carries out the calculating of infrared spectra detection and polymerization yield, detected result is as shown in table 2, the structure of the butadiene isoprene copolymer that table 2 obtains for the embodiment of the present invention 15～embodiment 28 and polymerization yield.
Embodiment 16
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 90:10; the rare-earth catalysis system that adds again embodiment 8 to prepare; at 50 ℃, carry out polyreaction 24 hours, the mole number that the consumption of described rare-earth catalysis system meets Yb in rare-earth catalysis system is 5 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 16 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 17
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 90:10; the rare-earth catalysis system that adds again embodiment 14 to prepare; at 50 ℃, carry out polyreaction 24 hours, the mole number that the consumption of described rare-earth catalysis system meets Yb in rare-earth catalysis system is 5 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 17 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 18
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 50:50; the rare-earth catalysis system that adds again embodiment 1 to prepare; at 60 ℃, carry out polyreaction 8 hours, the mole number that the consumption of described rare-earth catalysis system meets Nd in rare-earth catalysis system is 2 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 18 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 19
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 50:50; the rare-earth catalysis system that adds again embodiment 7 to prepare; at 60 ℃, carry out polyreaction 8 hours, the mole number that the consumption of described rare-earth catalysis system meets Nd in rare-earth catalysis system is 2 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 19 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 20
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, it is the butadiene-isoprene hexane solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 50:50; the rare-earth catalysis system that adds again embodiment 11 to prepare; at 60 ℃, carry out polyreaction 8 hours, the mole number that the consumption of described rare-earth catalysis system meets Yb in rare-earth catalysis system is 2 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 20 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 21
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 10:90; the rare-earth catalysis system that adds again embodiment 2 to prepare; at 80 ℃, carry out polyreaction 1 hour, the mole number that the consumption of described rare-earth catalysis system meets La in rare-earth catalysis system is 8 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 21 detects and the calculating of polymerization yield, and detected result is as shown in table 2.
Embodiment 22
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 10:90; the rare-earth catalysis system that adds again embodiment 9 to prepare; at 80 ℃, carry out polyreaction 1 hour, the mole number that the consumption of described rare-earth catalysis system meets Nd in rare-earth catalysis system is 8 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 22 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 23
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 10:90; the rare-earth catalysis system that adds again embodiment 13 to prepare; at 80 ℃, carry out polyreaction 1 hour, the mole number that the consumption of described rare-earth catalysis system meets La in rare-earth catalysis system is 8 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The present invention carries out the calculating of infrared spectra detection and polymerization yield by implementing 23 butadiene isoprene copolymers that obtain, and detected result is as shown in table 2.
Embodiment 24
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 30:70; the rare-earth catalysis system that adds again embodiment 3 to prepare; at 20 ℃, carry out polyreaction 15 hours, the mole number that the consumption of described rare-earth catalysis system meets Sm in rare-earth catalysis system is 1 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 24 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 25
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 30:70; the rare-earth catalysis system that adds again embodiment 6 to prepare; at 20 ℃, carry out polyreaction 15 hours, the mole number that the consumption of described rare-earth catalysis system meets Yb in rare-earth catalysis system is 1 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 25 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 26
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 30:70; the rare-earth catalysis system that adds again embodiment 10 to prepare; at 20 ℃, carry out polyreaction 15 hours, the mole number that the consumption of described rare-earth catalysis system meets La in rare-earth catalysis system is 1 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 26 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 27
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 80:20; the rare-earth catalysis system that adds again embodiment 4 to prepare; at 60 ℃, carry out polyreaction 10 hours, the mole number that the consumption of described rare-earth catalysis system meets Er in rare-earth catalysis system is 6 * 10 with the divinylic monomer adding with the ratio of isoprene monomer total mass
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 27 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
Embodiment 28
Under nitrogen protection; to adding 20mL mass concentration in the polymerizer of anhydrous and oxygen-free, be the butadiene-isoprene solution of 10g/100mL; in described solution, the mass ratio of divinylic monomer and isoprene monomer is 80:20; the rare-earth catalysis system that adds again embodiment 12 to prepare; at 60 ℃, carry out polyreaction 10 hours, the mole number that the consumption of described rare-earth catalysis system meets Nd in rare-earth catalysis system is 6 * 10 with the divinylic monomer adding with the ratio of the total mass of isoprene monomer
-6mol/g; The ethanolic soln of the BHT that is then 1% with mass concentration percentage ratio condenses polymkeric substance, by after the polymkeric substance washing obtaining, extruding, under 40 ℃, vacuum condition, is dried to constant weight, obtains butadiene isoprene copolymer.
The butadiene isoprene copolymer that the present invention obtains embodiment 28 carries out the calculating of infrared spectra detection and polymerization yield, and detected result is as shown in table 2.
The structure of the butadiene isoprene copolymer that table 2 embodiment of the present invention 15～embodiment 28 obtains and polymerization yield
As seen from the above embodiment, the invention provides a kind of rare-earth catalysis system, comprise rare earth oxide title complex and alkylaluminium cpd; Described rare earth oxide title complex has the chemical constitution shown in formula (I); Wherein, Ln is rare earth element; R is acidic cpd; L is to electronics ligand compound; 0 < x≤4; 0≤y≤3.Compared with prior art, the present invention uses as catalyzer without rare earth oxide being prepared into rare earth carboxylate and not needing to add muriate, also without rare earth oxide is made to rare earth chloride by complicated technique, as catalyzer, uses.The preparation process of rare-earth catalysis system provided by the invention is simple, easy and simple to handle, lower to the requirement of reaction conditions.In addition not chloride element in rare-earth catalysis system provided by the invention, the corrosion that can avoid chlorine element to bring to production unit.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.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 carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (14)
1. a rare-earth catalysis system, comprises rare earth oxide title complex and alkylaluminium cpd;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
2. rare-earth catalysis system according to claim 1, is characterized in that, described Ln comprises a kind of in lanthanum, neodymium, samarium, erbium and ytterbium.
3. rare-earth catalysis system according to claim 1, is characterized in that, described R comprises a kind of in carboxylic acid, hydrochloric acid and sulfonic acid.
4. rare-earth catalysis system according to claim 1, is characterized in that, described L comprises a kind of in alcohol compound, sulfoxide compound, nitrogenous compound and ester compound.
5. rare-earth catalysis system according to claim 1, is characterized in that, described alkylaluminium cpd comprises a kind of in trialkylaluminium and alkyl-al hydride.
6. rare-earth catalysis system according to claim 1, is characterized in that, the mol ratio of described rare earth oxide title complex rare earth elements and alkylaluminium cpd is 1:(20～60).
7. rare-earth catalysis system according to claim 1, is characterized in that, the volumetric molar concentration of described rare-earth catalysis system rare earth elements is 2 * 10
-5mol/mL～5 * 10
-5mol/mL.
8. rare-earth catalysis system according to claim 1, is characterized in that, the preparation method of described rare earth oxide title complex comprises the following steps:
By rare earth oxide, acidic cpd with give electronics ligand compound mixed grinding, the rare earth oxide title complex of the chemical constitution shown in (I) that obtains thering is formula.
9. rare-earth catalysis system according to claim 8, is characterized in that, the time of described grinding is 30 hours～200 hours.
10. a preparation method for rare-earth catalysis system, comprises the following steps:
Rare earth oxide title complex and alkylaluminium cpd are mixed, the mixed system obtaining is carried out to ripening, obtain rare-earth catalysis system;
Described rare earth oxide title complex has the chemical constitution shown in formula (I):
Ln
2O
3·xR·yL（I）；
Wherein, Ln is rare earth element;
R is acidic cpd;
L is to electronics ligand compound;
0＜x≤4；0≤y≤3。
11. methods according to claim 10, is characterized in that, the temperature of described ripening is 20 ℃～80 ℃;
The time of described ripening is 1 hour～24 hours.
The preparation method of 12. 1 kinds of butadiene isoprene copolymers, comprises the following steps:
Under the effect of catalyzer, under the condition of anhydrous and oxygen-free, divinylic monomer and isoprene monomer are carried out to polyreaction in organic solvent, obtain butadiene isoprene copolymer;
Described catalyzer is the rare-earth catalysis system that in claim 1～9, in the rare-earth catalysis system described in any one or claim 10～11 prepared by the method described in any one.
13. methods according to claim 12, is characterized in that, the ratio of the mole number of described Rare Earths in Catalyst element and divinylic monomer and isoprene monomer total mass is 1.0 * 10
-6mol/g～8.0 * 10
-6mol/g.
14. methods according to claim 12, is characterized in that, the temperature of described polyreaction is 20 ℃～80 ℃;
The time of described polyreaction is 1 hour～24 hours.
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| CN1295087A (en) * | 1999-11-05 | 2001-05-16 | 中国科学院长春应用化学研究所 | Arene-improved double-olefine polymerizing rare earth catalyst and its preparation |
| CN101906110A (en) * | 2010-08-18 | 2010-12-08 | 中国科学院长春应用化学研究所 | Phthalate neodymium electron donor complex, preparing method and rare earth catalyst thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295087A (en) * | 1999-11-05 | 2001-05-16 | 中国科学院长春应用化学研究所 | Arene-improved double-olefine polymerizing rare earth catalyst and its preparation |
| CN101906110A (en) * | 2010-08-18 | 2010-12-08 | 中国科学院长春应用化学研究所 | Phthalate neodymium electron donor complex, preparing method and rare earth catalyst thereof |
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| CN105777965A (en) * | 2016-05-24 | 2016-07-20 | 中国科学院长春应用化学研究所 | Cation rare earth central catalysis system, preparation method thereof and preparation method of diolefin polymer |
| CN105777965B (en) * | 2016-05-24 | 2018-06-29 | 中国科学院长春应用化学研究所 | A kind of preparation method of cation rare earth center catalyst system and catalyzing, preparation method and double olefin copolymer |
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