CN103709295B - A kind of rare-earth catalysis system and preparation method thereof and poly-pentadiene preparation method - Google Patents
A kind of rare-earth catalysis system and preparation method thereof and poly-pentadiene preparation method Download PDFInfo
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Abstract
The invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；Described rare earth oxide coordination chemistry consists of Ln2O3·xR·yL；Wherein Ln is rare earth element；R is acid compound；L is to electron donor ligand compound；0 < x≤4；0≤y≤3.Compared with prior art, the present invention, without rare earth oxide being made rare earth carboxylate and not needing to add chloride as catalyst use, uses as catalyst without rare earth oxide is made rare earth chloride by complicated technology.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, requires relatively low to reaction condition.In addition rare-earth catalysis system raw material provided by the invention is easy to get, and the process that catalysis pentadiene monomer generation polyreaction obtains poly-pentadiene is gentle, steady, has good application prospect.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to a kind of rare-earth catalysis system and preparation method thereof and poly-pentadiene preparation method.
Background technology
Pentadiene is a kind of important component that petroleum cracking generates in the co-product fraction of ethylene gained, and its content is only second to cyclopentadiene and isoprene in Crude products.deep process.Pentadiene monomer obtains poly-pentadiene by polyreaction, and this polymer has good mechanical performance, has a wide range of applications in synthetic rubber field.
Catalyst used during the poly-pentadiene of preparation mainly has Fe-series catalyst, cobalt series catalyst, chromium-based catalysts, vanadium series catalyst and rare-earth catalysis system, if the patent No. is that U.S. patents disclosing of US3824226 adopts cobalt system three-element catalytic system to prepare the method gathering pentadiene, prepare anti-1,2-poly-pentadiene；The United States Patent (USP) that the patent No. is US4168357 and US5066754 individually discloses the method adopting chromium system three-element catalytic system and the poly-pentadiene of vanadium system binary catalyst system preparation, and preparation has synthesized Isosorbide-5-Nitrae-poly-pentadiene；The Chinese patent that publication number is CN102190745 discloses the method that the preparation of a kind of Fe-series catalyst gathers pentadiene, and this Fe-series catalyst includes: isooctyl acid ferrum, alkyl aluminum compound and electron donor；The Chinese patent that application number is CN201010195218.9 discloses a kind of rare-earth catalysis system and preparation method thereof, this rare-earth catalysis system includes rare earth phenates, alkyl aluminum and chloride, its preparation method, for phenolic compound and alkyl aluminum to be reacted in organic solvent, obtains reaction solution；In described reaction solution, add rare earth chloride, after reaction, obtain rare earth phenates；Rare earth phenates, alkyl aluminum and chloride are mixed, is warming up to 0 DEG C～60 DEG C reactions, obtains rare-earth catalysis system.
Fe-series catalyst, cobalt series catalyst, chromium-based catalysts and the vanadium series catalyst ability of stereospecfic polymerization in the process of the poly-pentadiene of preparation is poor, rare-earth catalysis system is compared with them, the process of the poly-pentadiene of preparation has the stereospecfic polymerization ability of excellence, the poly-pentadiene of high-cis can be obtained, therefore suffered from the attention of people.But rare-earth catalysis system disclosed in prior art needs to prepare into rare earth oxide rare earth carboxylate and adds chloride as the 3rd component, or it is just active that rare earth oxide is made rare earth chloride, this rare earth carboxylate or the complicated process of preparation of rare earth chloride, complex operation, the technical parameters such as reaction pressure, temperature, time are required harsh, time-consuming, is unfavorable for the extensive use of rare earth catalyst.
Summary of the invention
In view of this, it is an object of the invention 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, requires relatively low to reaction condition, has good application prospect.
The invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；
Described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3XR yL(I)；
Wherein, Ln is rare earth element；
R is acid compound；
L is to electron donor ligand compound；
0 < x≤4；0≤y≤3.
Preferably, described Ln includes the one in lanthanum, neodymium, samarium, erbium and ytterbium.
Preferably, described R includes the one in carboxylic acid, hydrochloric acid and sulfonic acid.
Preferably, described L includes the one in alcohol compound, sulfoxide compound, aminated compounds and ester type compound.
Preferably, described alkyl aluminum compound includes the one in trialkylaluminium and alkyl-al hydride.
Preferably, the mol ratio of described rare earth oxide coordination compound rare earth elements and alkyl aluminum compound is 1:(20～60).
Preferably, the 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 coordination compound comprises the following steps:
By rare earth oxide, acid compound and give electron donor ligand compound mixed grinding, obtain having the rare earth oxide coordination compound of chemical composition shown in formula (I).
Preferably, the time of described grinding is 30 hours～200 hours.
The preparation method that the invention provides a kind of rare-earth catalysis system, comprises the following steps:
Rare earth oxide coordination compound and alkyl aluminum compound are mixed, the mixed system obtained is carried out ripening, obtains rare-earth catalysis system；
Described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3XR yL(I)；
Wherein, Ln is rare earth element；
R is acid compound；
L is to electron donor ligand compound；
0 < x≤4；0≤y≤3.
Preferably, the temperature of described ripening is 20 DEG C～80 DEG C；
The time of described ripening is 1 hour～24 hours.
The preparation method that the invention provides a kind of poly-pentadiene, comprises the following steps:
Under the effect of catalyst, anhydrous and oxygen-free when, pentadiene monomer is carried out in organic solvent polyreaction, obtains poly-pentadiene；
The rare-earth catalysis system that described catalyst is the rare-earth catalysis system described in technique scheme or prepared by the method described in technique scheme.
Preferably, the molal quantity of described Rare Earths in Catalyst element and the ratio of pentadiene monomer mass are 1.0 × 10-6Mol/g～8.0 × 10-6mol/g。
Preferably, the temperature of described polyreaction is 20 DEG C～80 DEG C；
The time of described polyreaction is 1 hour～24 hours.
The invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；Described rare earth oxide coordination compound has the chemical composition shown in formula (I)；Wherein, Ln is rare earth element；R is acid compound；L is to electron donor ligand compound；0 < x≤4；0≤y≤3.Compared with prior art, the present invention, without rare earth oxide being prepared into rare earth carboxylate and adding chloride as catalyst use, uses as catalyst without rare earth oxide is made rare earth chloride by complicated technique.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, and the requirement of reaction condition is relatively low.In addition rare-earth catalysis system raw material provided by the invention is easy to get, and the process that catalysis pentadiene monomer generation polyreaction obtains poly-pentadiene is gentle, steady, has good application prospect.
Test result indicate that, rare-earth catalysis system provided by the invention can prepare cis-Isosorbide-5-Nitrae-poly-pentadiene, trans-1,4-gather pentadiene, cis-1, the poly-pentadiene of the poly-pentadiene of 2-and trans-1,2-poly-four kinds of structures of pentadiene, the yield of poly-pentadiene is up to 60.1%.
Detailed description of the invention
The invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；
Described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3XR yL(I)；
Wherein, Ln is rare earth element；
R is acid compound；
L is to electron donor ligand compound；
0 < x≤4；0≤y≤3.
Compared with prior art, the present invention, without rare earth oxide being prepared into rare earth carboxylate and not needing to add chloride as catalyst use, uses as catalyst without rare earth oxide is made rare earth chloride by complicated technique.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, and the requirement of reaction condition is relatively low.
Rare-earth catalysis system provided by the invention includes rare earth oxide coordination compound, and described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3XR yL(I)；
Wherein, Ln is rare earth element, it is preferred to the one in lanthanum, neodymium, samarium, erbium and ytterbium；
R is acid compound, it is preferred to the one in carboxylic acid, hydrochloric acid (HCl) and sulfonic acid, more preferably formic acid (HCOOH), HCl and trifluoromethanesulfonic acid (HCF3SO3) in one；
L is to electron donor ligand compound, it is preferred to the one in alcohol compound, sulfoxide compound, aminated compounds and lipoid substance, more preferably isopropanol ((CH3)2CHOH), isooctanol ((CH3)2C(CH2)5OH), Hexalin, benzyl alcohol, dimethyl sulfoxide, diphenyl sulfoxide, ethamine, diethylamine, triethylamine ((CH3CH2)3N), n-butylamine (CH3(CH2)2NH2), N,N-dimethylformamide (C3H7NO), the one in TRI N BUTYL PHOSPHATE (TBP), triphenyl phosphate (TPP), diisobutyl phthalate (DBP) and o-phthalic acid dibutyl ester (DOP)；It most preferably is (CH3)2CHOH、(CH3)2C(CH2)5OH, Hexalin, dimethyl sulfoxide, diphenyl sulfoxide, (CH3CH2)3N、CH3(CH2)2NH2、C3H7One in NO, TBP, TPP, DBP and DOP；
0 < x≤4, it is preferred that 1≤x≤4；It is furthermore preferred that 1≤x≤3；
0≤y≤3, it is preferred that 1≤y≤2.
In the present invention, described rare earth oxide coordination compound preferably prepares by the following method:
By rare earth oxide, acid compound and give electron donor ligand compound mixed grinding, obtain having the rare earth oxide coordination compound of chemical composition shown in formula (I).
In the present invention, described rare earth oxide, acid compound and be preferably 1:x:y to the mol ratio of electron donor ligand compound, 0 < x≤4, it is preferred that 1≤x≤4, it is furthermore preferred that 1≤x≤3；0≤y≤3, it is preferred that 1≤y≤2.In the present invention, described rare earth oxide has the molecular formula shown in formula (II):
Ln2O3(II),
Ln in formula (II) is consistent with Ln described in technique scheme, does not repeat them here；In the present invention, described acid compound and kind and the acid compound described in technique scheme of giving electron donor ligand compound and consistent to the kind of electron donor ligand compound, do not repeat them here.The present invention is to described rare earth oxide, acid compound and does not have special restriction to the source of electron donor ligand compound, adopt the rare earth oxide of mentioned kind well known to those skilled in the art, acid compound and give electron donor ligand compound, as can by market buy acquisition.The method of described mixing and grinding is not had special restriction by the present invention, adopts the technical scheme of mixing well known to those skilled in the art and grinding；The present invention preferably by rare earth oxide, acid compound and give electron donor ligand compound mix in dismembyator, be ground, obtain having the rare earth oxide coordination compound of chemical composition shown in formula (I)；In the present invention, the time of described grinding is preferably 30 hours～200 hours, more preferably 60 hours～160 hours, it is most preferred that be 100 hours～120 hours.
After preparing rare earth oxide coordination compound, it is carried out elementary analysis test by the present invention, and test result shows that the chemical composition of rare earth oxide coordination compound prepared by the present invention is Ln2O3XR yL, 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 includes alkyl aluminum compound, and described alkyl aluminum compound is preferably the one in trialkylaluminium and alkyl-al hydride, more preferably diisobutylaluminium hydride (Al (i-Bu)2H), ADEH (AlEt2H), triisobutyl aluminium (Al (i-Bu)3) and triethyl aluminum (AlEt3) in one.The source of described alkyl aluminum compound is not had special restriction by the present invention, adopts the alkyl aluminum compound of mentioned kind well known to those skilled in the art, obtains as bought by market.
In the present invention, described rare-earth catalysis system preferably also includes organic solvent.The kind of described organic solvent is not had special restriction by the present invention, adopts organic solvent well known to those skilled in the art；In the present invention, described organic solvent is preferably alkane or aromatic hydrocarbon, more preferably C atomic number is the alkane of 5～8, it is most preferred that for hexane；The present invention adopts that the rare-earth catalysis system that hexane prepares as solvent is nontoxic, environmental protection.The source of described organic solvent is not had special restriction by the present invention, adopts the organic solvent of mentioned kind well known to those skilled in the art, obtains as bought by market.
In the present invention, the mol ratio of the rare earth element in described rare earth oxide coordination compound and alkyl aluminum compound is preferably 1:(20～60), more preferably 1:(30～50), it is most preferred that for 1:(35～45).In the present invention, the quality of described rare earth oxide coordination compound, alkyl aluminum compound and organic solvent makes the molar concentration of rare-earth catalysis system rare earth elements preferably reach 2 × 10-5Mol/mL～5 × 10-5Mol/mL, is more preferably up to 3 × 10-5Mol/mL～4 × 10-5mol/mL。
The preparation method that the invention provides a kind of rare-earth catalysis system, comprises the following steps:
Rare earth oxide coordination compound and alkyl aluminum compound are mixed, the mixed system obtained is carried out ripening, obtains rare-earth catalysis system；
Described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3XR yL(I)；
Wherein, Ln is rare earth element；
R is acid compound；
L is to electron donor ligand compound；
0 < x≤4；0≤y≤3.
Rare earth oxide coordination compound, alkyl aluminum compound are preferably added sequentially in reaction vessel to mix, then the mixed system obtained are carried out ripening by the present invention, obtain rare-earth catalysis system.In the present invention, described mixed system preferably also includes organic solvent, rare earth oxide coordination compound, alkyl aluminum compound and organic solvent are preferably added sequentially in reaction vessel to mix by the present invention, then the mixed system obtained is carried out ripening, obtain rare-earth catalysis system.In the present invention, the consumption of described organic solvent makes the molar concentration of the rare-earth catalysis system rare earth elements prepared be preferably 2 × 10-5Mol/mL～5 × 10-5Mol/mL, more preferably 3 × 10-5Mol/mL～4 × 10-5mol/mL.The method of described mixing is not had special restriction by the present invention, adopts the technical scheme of mixing well known to those skilled in the art.The present invention mixes preferably under the protection of nitrogen.
In the present invention, described rare earth oxide coordination compound, alkyl aluminum compound are consistent with the kind of rare earth oxide coordination compound, alkyl aluminum compound and organic solvent described in technique scheme and source with source with the kind of organic solvent, do not repeat them here.In the present invention, the ratio of the molal quantity of the molal quantity of described alkyl aluminum compound and rare earth oxide coordination compound rare earth elements is preferably (20～60): 1, more preferably (30～50): 1, it is most preferred that for (35～45): 1.
After obtaining the mixed system of rare earth oxide coordination compound and alkyl aluminum compound, described mixed system is carried out ripening by the present invention, obtains rare-earth catalysis system.In the present invention, the temperature of described ripening is preferably 20 DEG C～80 DEG C, more preferably 35 DEG C～65 DEG C, it is most preferred that be 45 DEG C～55 DEG C；The time of described ripening is preferably 1 hour～24 hours, more preferably 6 hours～18 hours, it is most preferred that be 10 hours～15 hours.
The preparation method that the invention provides a kind of poly-pentadiene, comprises the following steps:
Under the effect of catalyst, anhydrous and oxygen-free when, pentadiene monomer is carried out in organic solvent polyreaction, obtains poly-pentadiene；
The rare-earth catalysis system that described catalyst is the rare-earth catalysis system described in technique scheme or prepared by the method described in technique scheme.
Pentadiene monomer is preferably joined in organic solvent by the present invention, obtains pentadiene monomer solution, under the effect of catalyst, anhydrous and oxygen-free when, pentadiene monomer solution is carried out polyreaction, obtains poly-pentadiene；When more preferably in anhydrous and oxygen-free, catalyst is joined in above-mentioned pentadiene monomer solution and carry out polyreaction, obtain poly-pentadiene；Most preferably under the protection of nitrogen, and when anhydrous and anaerobic, add catalyst after adding above-mentioned pentadiene monomer solution in reaction vessel, carry out polyreaction, obtain poly-pentadiene.In the present invention, described reaction vessel is preferably polymerizer, more preferably the polymerizer of anhydrous, anaerobic.
In the present invention, the rare-earth catalysis system that described catalyst is the rare-earth catalysis system described in technique scheme or prepared by the method described in technique scheme.The kind of described organic solvent is not had special restriction by the present invention, adopts the poly-organic solvent used by pentadiene of preparation 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, it is also possible to different from the organic solvent described in technique scheme.In the present invention, described organic solvent is preferably alkane or aromatic hydrocarbon, more preferably C atomic number is the alkane of 5～8, it is most preferred that for hexane；The present invention adopts hexane as the solvent in above-mentioned polyreaction, and the process of the poly-pentadiene of preparation is nontoxic, environmental protection；The source of described organic solvent is not had special restriction by the present invention, adopts the organic solvent of mentioned kind well known to those skilled in the art, obtains as bought by market.In the present invention, the consumption of described organic solvent preferably makes the mass concentration of pentadiene monomer solution reach 8g/100mL～12g/100mL, is more preferably up to 9g/100mL～11g/100mL, it is most preferred that for 10g/100mL.In the present invention, the consumption of described catalyst makes the molal quantity of rare-earth catalysis system rare earth elements be preferably (1.0 × 10 with the mass ratio of pentadiene monomer-6～8.0 × 10-6): 1, more preferably (2.0 × 10-6～6.0 × 10-6): 1, it is most preferred that for (3.0 × 10-6～5.0 × 10-6): 1.
The method of described polyreaction is not had special restriction by the present invention, adopts the technical scheme of polyreaction well known to those skilled in the art；In the present invention, the temperature of described polyreaction is preferably 20 DEG C～80 DEG C, more preferably 35 DEG C～65 DEG C, it is most preferred that be 45 DEG C～55 DEG C；The time of described polyreaction is preferably 1 hour～24 hours, more preferably 4 hours～20 hours, it is most preferred that be 8 hours～16 hours, is the most preferably 10 hours～14 hours.
After described polyreaction completes, present invention preferably employs terminator and terminate described polyreaction, be settled out polymer, obtain poly-pentadiene；More preferably the above-mentioned polymer being settled out is adopted washing with alcohol, after washing is obtained product extruding, be dried to constant weight, obtain poly-pentadiene.In the present invention, described terminator is preferably BHT, more preferably the alcoholic solution of BHT；The mass concentration of the alcoholic solution of described BHT is preferably 0.5%～1.5%, more preferably 1%.Described washing, extruding and dry method are not had special restriction by the present invention, adopt washing well known to those skilled in the art, extruding and dry technical scheme；The present invention preferably in 35 DEG C～45 DEG C, be dried under vacuum condition.
The poly-pentadiene prepared is carried out nuclear-magnetism detection by the present invention, testing result shows, adopt rare-earth catalysis system provided by the invention can prepare cis-1,4-gather pentadiene, trans-1,4-gather pentadiene, cis-1, the poly-pentadiene of the poly-pentadiene of 2-and trans-1,2-poly-four kinds of structures of pentadiene.
The present invention calculates the yield of the poly-pentadiene prepared, and the computational methods of described yield are not had special restriction by the present invention, the method adopting calculated yield well known to those skilled in the art.Result of calculation shows, adopts the poly-pentadiene of rare-earth catalysis system provided by the invention preparation, and its yield reaches as high as 60.1%.
The invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；Described rare earth oxide coordination compound has the chemical composition shown in formula (I)；Wherein, Ln is rare earth element；R is acid compound；L is to electron donor ligand compound；0 < x≤4；0≤y≤3.Compared with prior art, the present invention, without rare earth oxide being prepared into rare earth carboxylate and not needing to add chloride as catalyst use, uses as catalyst without rare earth oxide is made rare earth chloride by complicated technique.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, and the requirement of reaction condition is relatively low.In addition rare-earth catalysis system raw material provided by the invention is easy to get, and the process that catalysis pentadiene monomer generation polyreaction obtains poly-pentadiene is gentle, steady, has good application prospect.
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1
By Nd2O3And HCF3SO3Join in dismembyator according to the ratio that mol ratio is 1:3, grind 30 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 1 is obtained by the present invention is tested, and testing result is as shown in table 1, and table 1 is the chemical composition of the rare earth oxide coordination compound that the embodiment of the present invention 1～embodiment 13 obtains.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.6 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L3Hexane solution 1.8mL, then in the mixed solution obtained, add the hexane of 1.2mL, the molar concentration obtaining rare earth element is 4 × 10-5The solution of mol/mL, solution ageing 8 hours at 60 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 2
By La2O3, HCOOH and (CH3)2CHOH joins in dismembyator according to the ratio that mol ratio is 1:4:3, grinds 60 hours, obtains rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 2 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.75 × 10-4Rare earth oxide coordination compound that mol above-mentioned prepares, the Al (i-Bu) of 2.0mol/L3Hexane solution 1.5mL, then in the mixed solution obtained, add the hexane of 1.5mL, the molar concentration obtaining rare earth element is 5 × 10-5The solution of mol/mL, solution ageing 24 hours at 20 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 3
By Sm2O3、HCF3SO3(CH3)2C(CH2)5OH joins in dismembyator according to the ratio that mol ratio is 1:1:2, grinds 90 hours, obtains rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 3 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the Al (i-Bu) of 2.0mol/L2H hexane solution 2.0mL, then in the mixed solution obtained, add the hexane of 2.0mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 1 hour at 80 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 4
By Er2O3, HCl and Hexalin join in dismembyator according to the ratio that mol ratio is 1:3:3, grind 120 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 4 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L2H hexane solution 2.4mL, then in the mixed solution obtained, add the hexane of 1.6mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 12 hours at 50 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 5
By Nd2O3, HCl and dimethyl sulfoxide join in dismembyator according to the ratio that mol ratio is 1:2:2, grind 150 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 5 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.75 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the Al (i-Bu) of 2.0mol/L3Hexane solution 1.5mL, then in the mixed solution obtained, add the hexane of 1.5mL, the molar concentration obtaining rare earth element is 5 × 10-5The solution of mol/mL, solution ageing 24 hours at 20 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 6
By Yb2O3、HCF3SO3Join in dismembyator according to the ratio that mol ratio is 1:2:3 with diphenyl sulfoxide, grind 180 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 6 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.6 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L3Hexane solution 1.8mL, then in the mixed solution obtained, add the hexane of 1.2mL, the molar concentration obtaining rare earth element is 4 × 10-5The solution of mol/mL, solution ageing 8 hours at 60 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 7
By Nd2O3, HCOOH and (CH3CH2)3N joins in dismembyator according to the ratio that mol ratio is 1:2:2, grinds 200 hours, obtains rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 7 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L2H hexane solution 2.4mL, then in the mixed solution obtained, add the hexane of 1.6mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 12 hours at 50 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 8
By Nd2O3、HCF3SO3And CH3(CH2)2NH2Join in dismembyator according to the ratio that mol ratio is 1:2:3, grind 200 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 8 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L2H hexane solution 2.4mL, then in the mixed solution obtained, add the hexane of 1.6mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 12 hours at 50 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 9
By La2O3, HCl and C3H7NO joins in dismembyator according to the ratio that mol ratio is 1:2:3, grinds 100 hours, obtains rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 9 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the Al (i-Bu) of 2.0mol/L2H hexane solution 2.0mL, then in the mixed solution obtained, add the hexane of 2.0mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 1 hour at 80 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 10
By Yb2O3、HCF3SO3Join in dismembyator according to the ratio that mol ratio is 1:3:3 with TBP, grind 80 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 10 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.6 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L3Hexane solution 1.8mL, then in the mixed solution obtained, add the hexane of 1.2mL, the molar concentration obtaining rare earth element is 4 × 10-5The solution of mol/mL, solution ageing 8 hours at 60 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 11
By Nd2O3, HCl and TPP join in dismembyator according to the ratio that mol ratio is 1:2:2, grind 60 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 11 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.75 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the Al (i-Bu) of 2.0mol/L3Hexane solution 1.5mL, then in the mixed solution obtained, add the hexane of 1.5mL, the molar concentration obtaining rare earth element is 5 × 10-5The solution of mol/mL, solution ageing 24 hours at 20 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 12
By La2O3、HCF3SO3Join in dismembyator according to the ratio that mol ratio is 1:3:1 with DBP, grind 160 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 12 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the Al (i-Bu) of 2.0mol/L2H hexane solution 2.0mL, then in the mixed solution obtained, add the hexane of 2.0mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 1 hour at 80 DEG C that will obtain, obtain rare-earth catalysis system.
Embodiment 13
By Yb2O3, HCOOH and DOP join in dismembyator according to the ratio that mol ratio is 1:2:3, grind 120 hours, obtain rare earth oxide coordination compound.
The rare earth oxide coordination compound that embodiment 13 is obtained by the present invention is tested, and testing result is as shown in table 1.
Under nitrogen protection, in dry catalyst preparation pipe, it is sequentially added into 0.4 × 10-4Rare earth oxide coordination compound that mol is above-mentioned to be prepared, the AlEt of 2.0mol/L2H hexane solution 2.4mL, then in the mixed solution obtained, add the hexane of 1.6mL, the molar concentration obtaining rare earth element is 2 × 10-5The solution of mol/mL, solution ageing 12 hours at 50 DEG C that will obtain, obtain rare-earth catalysis system.
The chemical composition of the rare earth oxide coordination compound that table 1 embodiment of the present invention 1～embodiment 13 obtains
Embodiment 14
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 2 prepares; carrying out polyreaction at 50 DEG C 12 hours, it is 4 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of La and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 14 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2, the structure of the poly-pentadiene that table 2 obtains for the embodiment of the present invention 14～embodiment 26 and yield.
Embodiment 15
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 5 prepares; carrying out polyreaction at 50 DEG C 12 hours, it is 4 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Nd and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 15 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 16
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 11 prepares; carrying out polyreaction at 50 DEG C 12 hours, it is 4 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Nd and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 16 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 17
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 1 prepares; carrying out polyreaction at 80 DEG C 1 hour, it is 8 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Nd and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 17 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 18
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 6 prepares; carrying out polyreaction at 80 DEG C 1 hour, it is 8 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Yb and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 18 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 19
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 10 prepares; carrying out polyreaction at 80 DEG C 1 hour, it is 8 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Yb and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 19 is obtained by the present invention carries out detecting and the calculating of yield, and testing result is as shown in table 2.
Embodiment 20
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 3 prepares; carrying out polyreaction at 20 DEG C 24 hours, it is 2 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Sm and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 20 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 21
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 9 prepares; carrying out polyreaction at 20 DEG C 24 hours, it is 2 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of La and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 21 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 22
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 12 prepares; carrying out polyreaction at 20 DEG C 24 hours, it is 2 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of La and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The present invention carries out the calculating of nuclear-magnetism detection and yield by implementing the 22 poly-pentadienes obtained, and testing result is as shown in table 2.
Embodiment 23
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 4 prepares; carrying out polyreaction at 60 DEG C 8 hours, it is 1 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Er and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 23 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 24
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 7 prepares; carrying out polyreaction at 60 DEG C 8 hours, it is 1 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Nd and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 24 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 25
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 8 prepares; carrying out polyreaction at 60 DEG C 8 hours, it is 1 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Nd and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 25 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
Embodiment 26
Under nitrogen protection; the pentadiene monomer hexane solution that 20mL mass concentration is 10g/100mL is added in the polymerizer of anhydrous and oxygen-free; add the rare-earth catalysis system that embodiment 13 prepares; carrying out polyreaction at 60 DEG C 8 hours, it is 1 × 10 that the consumption of described rare-earth catalysis system meets the ratio of the molal quantity of Yb and the pentadiene monomer mass of addition in rare-earth catalysis system-6mol/g；Then condense polymer with the alcoholic solution of the BHT that mass concentration percent is 1%, after the polymer washing obtained, extruding, in 40 DEG C, be dried to constant weight under vacuum condition, obtain poly-pentadiene.
The poly-pentadiene that embodiment 26 is obtained by the present invention carries out the calculating of nuclear-magnetism detection and yield, and testing result is as shown in table 2.
The structure of the poly-pentadiene that table 2 embodiment of the present invention 14～embodiment 26 obtains and yield
As seen from the above embodiment, the invention provides a kind of rare-earth catalysis system, including rare earth oxide coordination compound and alkyl aluminum compound；Described rare earth oxide coordination compound has the chemical composition shown in formula (I)；Wherein, Ln is rare earth element；R is acid compound；L is to electron donor ligand compound；0 < x≤4；0≤y≤3.Compared with prior art, the present invention, without rare earth oxide being prepared into rare earth carboxylate and using as catalyst without adding chloride, uses as catalyst without rare earth oxide is made rare earth chloride by complicated technique.Rare-earth catalysis system preparation process provided by the invention is simple, easy and simple to handle, and the requirement of reaction condition is relatively low.In addition rare-earth catalysis system raw material provided by the invention is easy to get, and the process that catalysis pentadiene monomer generation polyreaction obtains poly-pentadiene is gentle, steady, has good application prospect.
The explanation of above example is only intended to help to understand method and the core concept thereof 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, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a preparation method for poly-pentadiene, comprises the following steps:
Under the effect of catalyst, anhydrous and oxygen-free when, pentadiene monomer is carried out in organic solvent polyreaction, obtains poly-pentadiene；
Described catalyst is rare-earth catalysis system；
Described rare-earth catalysis system includes rare earth oxide coordination compound and alkyl aluminum compound；
Described rare earth oxide coordination compound has the chemical composition shown in formula (I):
Ln2O3·xR·yL(I)；
Wherein, Ln is rare earth element；
R is acid compound；
L is to electron donor ligand compound；
0 < x≤4；0≤y≤3.
2. method according to claim 1, it is characterised in that described Ln includes the one in lanthanum, neodymium, samarium, erbium and ytterbium.
3. method according to claim 1, it is characterised in that described R includes the one in carboxylic acid, hydrochloric acid and sulfonic acid.
4. method according to claim 1, it is characterised in that described L includes the one in alcohol compound, sulfoxide compound, aminated compounds and ester type compound.
5. method according to claim 1, it is characterised in that described alkyl aluminum compound includes the one in trialkylaluminium and alkyl-al hydride.
6. method according to claim 1, it is characterised in that the mol ratio of described rare earth oxide coordination compound rare earth elements and alkyl aluminum compound is 1:(20～60).
7. method according to claim 1, it is characterised in that the preparation method of described rare earth oxide coordination compound comprises the following steps:
By rare earth oxide, acid compound and give electron donor ligand compound mixed grinding, obtain having the rare earth oxide coordination compound of chemical composition shown in formula (I).
8. method according to claim 7, it is characterised in that the time of described grinding is 30 hours～200 hours.
9. method according to claim 1, it is characterised in that the molal quantity of described Rare Earths in Catalyst element and the ratio of pentadiene monomer mass are 1.0 × 10-6Mol/g～8.0 × 10-6mol/g。
10. method according to claim 1, it is characterised in that the temperature of described polyreaction is 20 DEG C～80 DEG C；
The time of described polyreaction is 1 hour～24 hours.
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