CN101974023A - Rare earth complex, catalyst, preparation method thereof and preparation method of polybutadiene - Google Patents
Rare earth complex, catalyst, preparation method thereof and preparation method of polybutadiene Download PDFInfo
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Abstract
The embodiment of the invention discloses a rare earth complex the molecular formula of which is Ln(CF3SO3)3.xH2O.yL. The invention also provides a rare earth sulfonate catalyst and a preparation method thereof. The rare earth sulfonate catalyst comprises aluminum alkyls and the rare earth complex, wherein the mol ratio of the aluminum alkyls to the Ln is 10-60:1. Besides, the invention also provides a preparation method of polybutadiene. The rare earth sulfonate catalyst provided by the invention has small corrosion behavior, thereby being environment friendly. The rare earth sulfonate catalyst provided by the invention provides a new catalysis system for the field of synthetic rubber. Experimental results indicate that the cis-content of the polybutadiene obtained by using the prepared rare earth sulfonate catalyst in the invention is high and can be up to 97% or above, and the weight-average molecular weight of the prepared polybutadiene is 4*10<5>-20*10<5>.
Description
Technical field
The present invention relates to technical field of polymer, more particularly, relate to the preparation method of a kind of rare earth compounding, Catalysts and its preparation method and polyhutadiene.
Background technology
Polybutadiene rubber is to be a kind of important synthetic rubber that monomer polymerization obtains with the 1,3-butadiene.According to the difference of microtexture, polybutadiene rubber is divided into cis-1,4 polybutadiene rubber, anti-form-1,4 polybutadiene rubbers, a cotype-1,2 polybutadiene rubber, full cotype-1,2 polybutadiene rubber, random formula-1,2 polybutadiene rubber etc.Wherein, in the polybutadiene rubber of various microtextures, the excellent combination property of cis-1,4 polybutadiene rubber have characteristics such as lower glass transition temperatures, high adhesion, snappiness and high abrasion resistance, and high more its performance of cis-structure is excellent more.
In the preparation process of cis-polybutadiene, catalyzer is the important factor of the polybutadiene configuration content of influence preparation.At present, reported multiple preparation method about cis-polybutadiene, for example, the patent No. is that the american documentation literature of US3499882 has reported that adopting titanium is the polyhutadiene method that catalyst system prepares cis; The patent No. is that the american documentation literature of US3993856 and Chinese patent literature that publication number is CN1170005 have reported that adopting cobalt is the method that catalyst system is prepared the polyhutadiene of cis; Publication number is that the Chinese patent literature of CN1693321A and CN1196723C and american documentation literature that the patent No. is US0020045721 have reported that adopting nickel is the method that catalyst system prepares cis-polybutadiene.But adopting titanium in the above-mentioned report is that catalyst system, cobalt are that catalyst system or nickel are the method for catalyst system as the Preparation of Catalyst polyhutadiene, and the cis-structure of the polyhutadiene for preparing is relatively low, thereby over-all properties is relatively poor.
With titanium is that catalyst system, cobalt are that catalyst system is that catalyst system is compared with nickel, and rare-earth catalysis system causes people's extensive concern owing to producing higher cis microstructure.For example, adopting neodymium is the polybutadiene rubber excellent performance that catalyst system prepares, and can be good at being applied in the fields such as tire, golf ball and high-impact polystyrene.The patent No. is that the European patent document of EP1055659A1 and american documentation literature that the patent No. is US6482906 have reported that the neodymium that adopts neodecanoic acid neodymium, aluminum alkyls and halogen to form is that the catalyst system polymerization obtains high-cis polybutadiene.In above-mentioned report, this neodymium is that catalyst system employing halogen simple substance is necessary component, thereby this catalyst system has stronger corrosive nature, has polluted environment.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation method of a kind of rare earth compounding, Catalysts and its preparation method and polyhutadiene, the not halogen-containing simple substance of catalyzer provided by the invention, no corrosive nature is utilized the cis-content height of the polyhutadiene of this Preparation of Catalyst.
The invention provides a kind of rare earth compounding, its molecular formula is Ln (CF
3SO
3)
3XH
2OyL,
Wherein, Ln is a rare earth element, and L is to the electronics part, 0＜x≤8,1≤y≤4.
Preferably, described rare earth element is lanthanum, neodymium, samarium, erbium or ytterbium.
Preferably, described is alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound to the electronics part.
The present invention also provides a kind of sulfoacid rare earth catalyst, comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1.
Preferably, described rare earth element is lanthanum, neodymium, samarium, erbium or ytterbium.
Preferably, described is alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound to the electronics part.
Preferably, described alcohol compound is an ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, isooctyl alcohol, hexalin or phenylcarbinol, described sulfoxide compound is dimethyl sulfoxide (DMSO) or diphenyl sulfoxide, described furfuran compound is a tetrahydrofuran (THF), 2-bromine furans or 2, the 5-dibrom furan, described aminated compounds is an ethamine, diethylamine, triethylamine, n-Butyl Amine 99 or N, dinethylformamide, described ether compound is a methyl ethyl ether, ether, positive propyl ether or n-butyl ether, described ester compound are TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
Preferably, described aluminum alkyls is diisobutylaluminium hydride Al (i-Bu)
2H or triisobutyl aluminium Al (i-Bu)
3
The present invention also provides a kind of preparation method of sulfoacid rare earth catalyst, comprising:
With the trifluoromethanesulfonic acid rare earth compound, give electronics part and solvent, heating obtains the trifluoromethanesulfonic acid rare earth compounding, described rare earth element is 1: 3～10 with described mol ratio to the electronics part;
Described trifluoromethanesulfonic acid rare earth compounding and aluminum alkyls are mixed, obtain sulfoacid rare earth catalyst, the mol ratio of the rare earth element in described aluminum alkyls and the trifluoromethanesulfonic acid rare earth compounding is 10～60: 1.
The present invention also provides a kind of preparation method of polyhutadiene, comprising:
The alkane solution and the sulfoacid rare earth catalyst of divinyl are mixed, react under 0～70 ℃ of condition, obtain polyhutadiene, described sulfoacid rare earth catalyst comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The trifluoromethanesulfonic acid rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1, described rare earth element is 1.0 * 10 with the molar mass ratio of described divinyl
-5～9.0 * 10
-5Mol: 1g.
From above-mentioned technical scheme as can be seen, the invention provides a kind of rare earth compounding, its molecular formula is Ln (CF
3SO
3)
3XH
2OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4.The present invention also provides a kind of sulfoacid rare earth catalyst and preparation method thereof, and this sulfoacid rare earth catalyst comprises aluminum alkyls and above-mentioned rare earth compounding, and wherein, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1.In addition, the present invention also provides a kind of preparation method of polyhutadiene, is catalyzer with above-mentioned sulfoacid rare earth catalyst, prepares polyhutadiene.Because the not halogen-containing simple substance of sulfoacid rare earth catalyst provided by the invention, therefore, the corrosive nature of catalyzer is less, has protected environment.Sulfoacid rare earth catalyst provided by the invention has enriched the kind of catalyst system for the synthetic rubber field has increased a catalyst system.Experimental result shows that the cis-content height of the polyhutadiene that the sulfoacid rare earth catalyst that utilizes the present invention to prepare prepares reaches more than 97%, and the weight-average molecular weight of the polyhutadiene of preparation is 4 * 10
5～20 * 10
5
Embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
The invention discloses a kind of rare earth compounding, its molecular formula is Ln (CF
3SO
3)
3XH
2OyL,
Wherein, Ln is a rare earth element, and L is to the electronics part, 0＜x≤8,1≤y≤4.
In the above-mentioned rare earth compounding, described rare earth element is preferably lanthanum, neodymium, samarium, erbium or ytterbium, and the described electronics part of giving is preferably alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound.Wherein, described alcohol compound is preferably straight chain alcohol, branched-chain alcoho or aromatic alcohol, and object lesson can be ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, isooctyl alcohol, hexalin or phenylcarbinol.Described sulfoxide compound is preferably dimethyl sulfoxide (DMSO) or diphenyl sulfoxide.Described furfuran compound is preferably tetrahydrofuran (THF), 2-bromine furans or 2,5-dibrom furan.Described aminated compounds is preferably ethamine, diethylamine, triethylamine, n-Butyl Amine 99 or N, dinethylformamide.Described ether compound is preferably methyl ethyl ether, ether, positive propyl ether or n-butyl ether.Described ester compound is preferably TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
The present invention also provides a kind of sulfoacid rare earth catalyst, comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1.
In the above-mentioned rare earth compounding, described rare earth element is preferably lanthanum, neodymium, samarium, erbium or ytterbium, and the described electronics part of giving is preferably alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound.Described aluminum alkyls is diisobutylaluminium hydride Al (i-Bu)
2H or triisobutyl aluminium Al (i-Bu)
3The mol ratio of described aluminum alkyls and described Ln is 10～60: 1, is preferably 20～50: 1, more preferably 30～50: 1.
The present invention also provides a kind of preparation method of sulfoacid rare earth catalyst, comprising:
With the trifluoromethanesulfonic acid rare earth compound, give electronics part and solvent, heating obtains the trifluoromethanesulfonic acid rare earth compounding, described rare earth element is 1: 3～10 with described mol ratio to the electronics part;
Described trifluoromethanesulfonic acid rare earth compounding and aluminum alkyls are mixed, obtain sulfoacid rare earth catalyst, the mol ratio of the rare earth element in described aluminum alkyls and the trifluoromethanesulfonic acid rare earth compounding is 10～60: 1.
Above-mentioned trifluoromethanesulfonic acid rare earth compound preferably is prepared as follows:
Rare earth oxide and trifluoromethanesulfonic acid are mixed, be heated to 40～80 ℃, reacted 2～10 hours, obtain the trifluoromethanesulfonic acid rare earth compound, the mol ratio of described rare earth oxide and trifluoromethanesulfonic acid is preferably 8～12: 1, and more preferably 10: 1.Described trifluoromethanesulfonic acid preferably reacts with the form of the aqueous solution.Described rare earth oxide and trifluoromethanesulfonic acid mix, and specifically are preferably: rare earth oxide is joined in the trifluoromethanesulfonic acid solution, stir.
In addition, above-mentionedly preferably include in addition after preparing sulfoacid rare earth catalyst: add hexane, being made into concentration is 1～9 * 10
-5The catalyzer of mol/ml was in 40～60 ℃ of following ageings 10～20 hours.
Above-mentioned trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is preferably lanthanum, neodymium, samarium, erbium or ytterbium, and the described electronics part of giving is preferably alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound.The present invention is to solvent and have no special requirements, and object lesson can be tetrahydrofuran (THF).
Described with the trifluoromethanesulfonic acid rare earth compound, to electronics part and solvent, heating is specifically as follows:
Described with the trifluoromethanesulfonic acid rare earth compound with to the mixing of electronics part, the adding tetrahydrofuran (THF), heating, condensing reflux 5～24h boils off solvent under the solution boiling state, and drying obtains the trifluoromethanesulfonic acid rare earth compounding.
In above-mentioned trifluoromethanesulfonic acid rare earth compounding process, described rare earth element and described to give the mol ratio of electronics part be 1: 3～10, be preferably 1: 5～10, more preferably 1: 6～9.The mol ratio of the rare earth element in described aluminum alkyls and the trifluoromethanesulfonic acid rare earth compounding is 10～60: 1, is preferably 20～60: 1, more preferably 30～60: 1.
In addition, the present invention also provides a kind of preparation method of polyhutadiene, comprising:
The alkane solution and the sulfoacid rare earth catalyst of divinyl are mixed, react under 0～70 ℃ of condition, obtain polyhutadiene, described sulfoacid rare earth catalyst comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The trifluoromethanesulfonic acid rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1,
Described rare earth element is 1.0 * 10 with the molar mass ratio of described divinyl
-5～9.0 * 10
-5Mol: 1g.
According to the present invention, above-mentioned preparation process is preferably carried out under nitrogen protection.Described alkane is preferably hexane.The described reaction times of reacting under 0～70 ℃ of condition is preferably 0.5～24 hour, more preferably 2～24 hours.
According to the present invention, the preparation method of above-mentioned polyhutadiene also preferably includes:
With 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol obtains polyhutadiene;
Described polyhutadiene is pushed the final vacuum drying through washing with alcohol.
Described 2, the massfraction of the ethanolic soln of 6-di-tert-butyl methyl phenol is preferably 0.8%～2%, and more preferably 1%.
From technique scheme as can be seen, the invention provides the preparation method of a kind of rare earth compounding, Catalysts and its preparation method and polyhutadiene.Catalyzer provided by the invention is made up of trifluoromethanesulfonic acid rare earth compounding and aluminum alkyls, not halogen-containing simple substance, and no corrosive nature is utilized the cis-content height of the polyhutadiene of this Preparation of Catalyst.Sulfoacid rare earth catalyst provided by the invention has enriched the kind of catalyst system for the synthetic rubber field has increased new catalyst system.
In order to further specify technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment 1
The preparation of trifluoromethanesulfonic acid neodymium
In reactor, be that 10: 1 ratio joins Neodymium trioxide in the trifluoromethanesulfonic acid solution according to the mol ratio of Neodymium trioxide and trifluoromethanesulfonic acid, be heated to 70 ℃ under the agitation condition, reacted 8 hours, filter, the unreacted Neodymium trioxide is removed, concentrate the trifluoromethanesulfonic acid neodymium aqueous solution, the spissated trifluoromethanesulfonic acid neodymium aqueous solution is put in separates out crystal under the room temperature naturally again, be the trifluoromethanesulfonic acid neodymium of band crystal water.
Embodiment 2
The preparation of trifluoromethanesulfonic acid lanthanum
In reactor, be that 10: 1 ratio joins lanthanum trioxide in the trifluoromethanesulfonic acid solution according to the mol ratio of lanthanum trioxide and trifluoromethanesulfonic acid, be heated to 70 ℃ under the agitation condition, reacted 8 hours, filter, the unreacted lanthanum trioxide is removed, concentrate the trifluoromethanesulfonic acid lanthanum aqueous solution, the spissated trifluoromethanesulfonic acid lanthanum aqueous solution is put in separates out crystal under the room temperature naturally again, be the trifluoromethanesulfonic acid lanthanum of band crystal water.
Embodiment 3
The preparation of trifluoromethanesulfonic acid samarium
In reactor, be that 10: 1 ratio joins Samarium trioxide in the trifluoromethanesulfonic acid solution according to the mol ratio of Samarium trioxide and trifluoromethanesulfonic acid, be heated to 70 ℃ under the agitation condition, reacted 8 hours, filter, the unreacted Samarium trioxide is removed, concentrate the trifluoromethanesulfonic acid samarium aqueous solution, the spissated trifluoromethanesulfonic acid samarium aqueous solution is put in separates out crystal under the room temperature naturally again, be the trifluoromethanesulfonic acid samarium of band crystal water.
Embodiment 4
The preparation of trifluoromethanesulfonic acid erbium
In reactor, be that 10: 1 ratio joins Erbium trioxide in the trifluoromethanesulfonic acid solution according to the mol ratio of Erbium trioxide and trifluoromethanesulfonic acid, be heated to 70 ℃ under the agitation condition, reacted 8 hours, filter, the unreacted Erbium trioxide is removed, concentrate the trifluoromethanesulfonic acid erbium aqueous solution, the spissated trifluoromethanesulfonic acid erbium aqueous solution is put in separates out crystal under the room temperature naturally again, be the trifluoromethanesulfonic acid erbium of band crystal water.
Embodiment 5
The preparation of Ytterbiumtriflate
In reactor, be that 10: 1 ratio joins ytterbium oxide in the trifluoromethanesulfonic acid solution according to the mol ratio of ytterbium oxide and trifluoromethanesulfonic acid, be heated to 70 ℃ under the agitation condition, reacted 8 hours, filter, the unreacted ytterbium oxide is removed, concentrate the Ytterbiumtriflate aqueous solution, the spissated Ytterbiumtriflate aqueous solution is put in separates out crystal under the room temperature naturally again, be the Ytterbiumtriflate of band crystal water.
Embodiment 6～15
The preparation of trifluoromethanesulfonic acid rare earth alcohols title complex
In rare earth: the mol ratio of giving the electronics ligand L is that 1: 3 ratio is respectively the trifluoromethanesulfonic acid rare earth compound of embodiment 1～5 preparation with add in the reactor for the electronics ligand L, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 16h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain the title complex of table 1 respectively.The trifluoromethanesulfonic acid rare earth alcohols title complex for preparing carries out ultimate analysis, and this measuring method is suitable equally for embodiment 16～32, and results of elemental analyses is as shown in table 7.
Table 1 is given the alcohol compound of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
Embodiment 16
In lanthanum: the mol ratio of dimethyl sulfoxide (DMSO) is that 1: 3 ratio adds the trifluoromethanesulfonic acid lanthanum of embodiment 2 preparations and dimethyl sulfoxide (DMSO) in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 18h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 2.
Embodiment 17
In ytterbium: the mol ratio of diphenyl sulfoxide is that 1: 3 ratio adds the Ytterbiumtriflate of embodiment 5 preparations and diphenyl sulfoxide in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 18h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 2.
Table 2 is given the sulfone compound of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
Embodiment 18
In neodymium: the mol ratio of tetrahydrofuran (THF) is that 1: 10 ratio adds the trifluoromethanesulfonic acid neodymium of embodiment 1 preparation and tetrahydrofuran (THF) in the reactor respectively, condensing reflux 24h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 3.
Embodiment 19
In samarium: the mol ratio of 2-bromine furans is that 1: 10 ratio adds the trifluoromethanesulfonic acid samarium of embodiment 3 preparations and 2-bromine furans in the reactor respectively, condensing reflux 24h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 3.
Embodiment 20
Press erbium: 2, the mol ratio of 5-dibrom furan is the trifluoromethanesulfonic acid erbium and 2 that 1: 10 ratio prepares embodiment 4 respectively, the 5-dibrom furan adds in the reactor, condensing reflux 24h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 3.
Table 3 is given the furfuran compound of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
Embodiment 21
In neodymium: the mol ratio of ethamine is that 1: 5 ratio adds the trifluoromethanesulfonic acid neodymium of embodiment 1 preparation and ethamine in the reactor respectively, and condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtains rare earth compounding, and is as shown in table 4.
Embodiment 22
In lanthanum: the mol ratio of diethylamine is that 1: 5 ratio adds the trifluoromethanesulfonic acid lanthanum of embodiment 2 preparations and diethylamine in the reactor respectively, condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 4.
Embodiment 23
In samarium: the mol ratio of triethylamine is that 1: 5 ratio adds the trifluoromethanesulfonic acid samarium of embodiment 3 preparations and triethylamine in the reactor respectively, condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 4.
Embodiment 24
In ytterbium: the mol ratio of n-Butyl Amine 99 is that 1: 5 ratio adds the Ytterbiumtriflate of embodiment 5 preparations and n-Butyl Amine 99 in the reactor respectively, condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 4.
Embodiment 25
Press erbium: N, the mol ratio of dinethylformamide is trifluoromethanesulfonic acid erbium and the N that 1: 5 ratio prepares embodiment 4 respectively, dinethylformamide adds in the reactor, condensing reflux 15h under the solution boiling state, boil off solvent, and be dried to constant weight, and obtain rare earth compounding, as shown in table 4.
Table 4 is given the aminated compounds of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
Embodiment 26
In neodymium: the mol ratio of methyl ethyl ether is that 1: 10 ratio adds the trifluoromethanesulfonic acid neodymium of embodiment 1 preparation and methyl ethyl ether in the reactor respectively, condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 5.
Embodiment 27
In ytterbium: the mol ratio of ether is that 1: 10 ratio adds the Ytterbiumtriflate of embodiment 5 preparations and ether in the reactor respectively, and condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtains rare earth compounding, and is as shown in table 5.
Embodiment 28
In samarium: the mol ratio of positive propyl ether is that 1: 10 ratio adds the trifluoromethanesulfonic acid samarium of embodiment 3 preparations and positive propyl ether in the reactor respectively, condensing reflux 15h boils off solvent under the solution boiling state, and is dried to constant weight, obtain rare earth compounding, as shown in table 5.
Table 5 is given the ether compound of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
Embodiment 29
In neodymium: the mol ratio of TRI N BUTYL PHOSPHATE is that 1: 3 ratio adds trifluoromethanesulfonic acid neodymium and TRI N BUTYL PHOSPHATE in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 10h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 6.
Embodiment 30
In lanthanum: the mol ratio of triphenylphosphate is that 1: 3 ratio adds trifluoromethanesulfonic acid lanthanum and triphenylphosphate in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 10h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 6.
Embodiment 31
In samarium: the mol ratio of diisobutyl phthalate is that 1: 3 ratio adds trifluoromethanesulfonic acid samarium and diisobutyl phthalate in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 10h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 6.
Embodiment 32
In ytterbium: the mol ratio of dioctyl phthalate (DOP) is that 1: 3 ratio adds Ytterbiumtriflate and dioctyl phthalate (DOP) in the reactor respectively, add the 40ml tetrahydrofuran (THF) again as solvent, condensing reflux 10h under the solution boiling state, boil off solvent, and be dried to constant weight, obtain rare earth compounding, as shown in table 6.
Table 6 is given the ester compound of electronics part and the complex structure formula that the trifluoromethanesulfonic acid rare earth forms
The foregoing description is carried out ultimate analysis, and analytical results is as shown in table 7.
Each embodiment results of elemental analyses of table 7
Embodiment 33～37
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 1.2mL
2The H hexane solution, wherein the mol ratio of diisobutylaluminium hydride and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 60: 1, adds the 0.8mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 50 ℃ of following ageings 15 hours, obtains sulfoacid rare earth catalyst;
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst of preparation, and the mole number of the Nd of this catalyst system is 5 * 10 with adding monomeric quality g ratio
-5Mol/g, under 50 ℃ of conditions the reaction 7 hours, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that settles out in ethanol is after the washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight, and the result is as shown in table 8.The polymer yield of the polyhutadiene of present embodiment preparation is measured as follows:
The electronic balance weighing resulting polymers, calculated yield.The measuring method of above-mentioned polymer yield is suitable equally for embodiment 38～59.
The weight-average molecular weight of the polyhutadiene of present embodiment preparation is measured as follows:
With the gel permeation chromatograph that U.S. Waters company produces, polymkeric substance is diluted to 0.15～0.20mg/mL, and 0.45 μ m strainer filters.The GPC process software is Empower Pro, and solvent is THF, and flow velocity 1.0mL/min, polystyrene are interior mark, K=0.000246, and α=0.732, probe temperature is 30 ℃.Above-mentioned measuring method to the polymkeric substance weight-average molecular weight is suitable equally for embodiment 38～59.
Suitable-1,4 structural content of the polyhutadiene of present embodiment preparation is measured as follows:
Adopt polymkeric substance Fourier transform infrared spectroscopy (FTIR) analysis: polymkeric substance is dissolved in the dithiocarbonic anhydride (2～8mg/mL), film on the bromination sylvite plate, record on the Nicolet is10 infrared spectrometer with U.S. Thermo Electron Scientific Instruments LLC company, calculate the microtexture of polymkeric substance as follows:
A＝17667×D
738+3673.8×D
911+4741.4×D
967
cis-1，4(％)＝(17667×D
738/A)×100
1，2(％)＝(3673.8×D
911/A)×100
trans-1，4(％)＝(4741.4×D
967/A)×100
Wherein, D
738, D
911, D
967Be absorption band 738cm
-1, 911cm
-1, 976cm
-1Pairing absorption intensity.
The measuring method of suitable-1,4 structural content of above-mentioned polymkeric substance is suitable equally for embodiment 38～59.
Table 8 embodiment 33-37 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 33 | See embodiment 6 | 46.2 | 53 | 97.1 |
| Embodiment 34 | See embodiment 18 | 41.9 | 49 | 97.3 |
| Embodiment 35 | See embodiment 21 | 62.3 | 61 | 97.4 |
| Embodiment 36 | See embodiment 26 | 54.7 | 55 | 97.3 |
| Embodiment 37 | See embodiment 27 | 43.1 | 57 | 97.2 |
Embodiment 38-42
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.6mL
3Hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 30: 1, adds the 1.4mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 70 ℃ of following ageings 10 minutes, obtains sulfoacid rare earth catalyst;
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 8 * 10 with adding monomeric quality g ratio
-5Mol/g, under 50 ℃ of conditions the reaction 10 hours, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that settles out in ethanol is after the washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight, the results are shown in Table 9.
Table 9 embodiment 38-42 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 38 | See embodiment 7 | 56.6 | 109 | 97.5 |
| Embodiment 39 | See embodiment 8 | 70.9 | 112 | 97.7 |
| Embodiment 40 | See embodiment 19 | 50.3 | 98 | 97.8 |
| Embodiment 41 | See embodiment 20 | 59.7 | 102 | 97.6 |
| Embodiment 42 | See embodiment 22 | 63.1 | 85 | 97.7 |
Embodiment 43-46
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.4mL
3Hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 20: 1, adds the 1.6mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 50 ℃ of following ageings 5 hours, obtains sulfoacid rare earth catalyst;
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 3 * 10 with adding monomeric quality g ratio
-5Mol/g, reaction is 24 hours under 0 ℃ of condition, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that in ethanol, settles out, after washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight.The results are shown in Table 10.
Table 10 embodiment 43-46 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 43 | See embodiment 9 | 69.3 | 125 | ?98.2 |
| Embodiment 44 | See embodiment 10 | 70.1 | 131 | ?98.5 |
| Embodiment 45 | See embodiment 11 | 59.5 | 129 | ?98.3 |
| Embodiment 46 | See embodiment 28 | 63.4 | 127 | ?98.2 |
Embodiment 47～49
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.2mL
2The H hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 10: 1, adds the 1.8mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 0 ℃ of following ageing 24 hours, obtains sulfoacid rare earth catalyst;
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 9 * 10 with adding monomeric quality g ratio
-5Mol/g, reaction is 5 hours under 70 ℃ of conditions, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that in ethanol, settles out, after washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight.The results are shown in Table 11.
Table 11 embodiment 47-49 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 47 | See embodiment 12 | 68.9 | 136 | ?98.6 |
| Embodiment 48 | See embodiment 13 | 71.2 | 144 | ?98.3 |
| Embodiment 49 | See embodiment 30 | 67.2 | 142 | ?98.5 |
Embodiment 50～53
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.2mL
2The H hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 20: 1, adds the 1.8mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 40 ℃ of following ageings 1 hour, obtains sulfoacid rare earth catalyst.
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 7 * 10 with adding monomeric quality g ratio
-5Mol/g, under 50 ℃ of conditions the reaction 0.5 hour, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that settles out in ethanol is after the washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight.The results are shown in Table 12.
Table 12 embodiment 50-53 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 50 | See embodiment 14 | 63.6 | 152 | ?98.5 |
| Embodiment 51 | See embodiment 15 | 67.8 | 137 | ?98.3 |
| Embodiment 52 | See embodiment 17 | 78.2 | 146 | 98.4 |
| Embodiment 53 | See embodiment 23 | 79.1 | 140 | 98.2 |
Embodiment 54～56
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.2mL
2The H hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 20: 1, adds the 1.8mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 40 ℃ of following ageings 2 hours, obtains sulfoacid rare earth catalyst;
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 1 * 10 with adding monomeric quality g ratio
-5Mol/g, reaction is 5 hours under 50 ℃ of conditions, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that in ethanol, settles out, after washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight.The results are shown in Table 13.
Table 13 embodiment 54-56 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) | |
| Embodiment 54 | See embodiment 24 | 74.3 | 168 | ?98.7 |
| Embodiment 55 | See embodiment 31 | 84.8 | 191 | ?98.8 |
| Embodiment 56 | See embodiment 16 | 65.8 | 151 | ?98.5 |
Embodiment 57-59
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add 4 * 10 successively
-5The Al (i-Bu) of the 2.0mol/L of mol trifluoromethanesulfonic acid rare earth compounding, 0.2mL
3Hexane solution, wherein the mol ratio of aluminium isobutyl and trifluoromethanesulfonic acid rare earth compounding middle-weight rare earths element is 20: 1, adds the 1.8mL hexane, and being made into concentration is 2 * 10
-5The catalyzer of mol/ml in 50 ℃ of following ageings 1 hour, obtains sulfoacid rare earth catalyst.
Under nitrogen protection, adding the 20ml monomer concentration in the polymerizer of anhydrous and oxygen-free is 20g/100ml divinyl hexane solution, then adds the sulfoacid rare earth catalyst system of preparation, and the mole number of the Nd of this catalyst system is 8 * 10 with adding monomeric quality g ratio
-5Mol/g, reaction is 5 hours under 40 ℃ of conditions, with contain massfraction be 1% 2, the ethanolic soln termination reaction of 6-di-tert-butyl methyl phenol, the polymkeric substance that in ethanol, settles out, after washing with alcohol extruding, vacuum-drying obtains high-cis polybutadiene to constant weight.The results are shown in Table 14.
Table 14 embodiment 57-59 resulting polymers experimental result
| Title complex | Polymer yield (%) | Weight-average molecular weight (ten thousand) | Suitable-1,4 structural content (%) |
| Embodiment 57 | See embodiment 25 | 75.8 | 157 | ?98.6 |
| Embodiment 58 | See embodiment 29 | 90.6 | 173 | ?98.9 |
| Embodiment 59 | See embodiment 32 | 87.2 | 164 | ?98.3 |
From the foregoing description as can be seen, the invention provides the preparation method of a kind of rare earth compounding, Catalysts and its preparation method and polyhutadiene, experimental result shows, the cis-content height of the polyhutadiene that the sulfoacid rare earth catalyst that utilizes the present invention to prepare prepares, reach more than 97%, the weight-average molecular weight of the polyhutadiene of preparation is 4 * 10
5～20 * 10
5
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. rare earth compounding, its molecular formula is Ln (CF
3SO
3)
3XH
2OyL,
Wherein, Ln is a rare earth element, and L is to the electronics part, 0＜x≤8,1≤y≤4.
2. rare earth compounding according to claim 1 is characterized in that, described rare earth element is lanthanum, neodymium, samarium, erbium or ytterbium.
3. rare earth compounding according to claim 1 is characterized in that, described is alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound to the electronics part.
4. a sulfoacid rare earth catalyst is characterized in that, comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1.
5. sulfoacid rare earth catalyst according to claim 4 is characterized in that, described rare earth element is lanthanum, neodymium, samarium, erbium or ytterbium.
6. sulfoacid rare earth catalyst according to claim 4 is characterized in that, described is alcohol compound, sulfoxide compound, furfuran compound, aminated compounds, ether compound or ester compound to the electronics part.
7. sulfoacid rare earth catalyst according to claim 6, it is characterized in that, described alcohol compound is an ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, isooctyl alcohol, hexalin or phenylcarbinol, described sulfoxide compound is dimethyl sulfoxide (DMSO) or diphenyl sulfoxide, described furfuran compound is a tetrahydrofuran (THF), 2-bromine furans or 2, the 5-dibrom furan, described aminated compounds is an ethamine, diethylamine, triethylamine, n-Butyl Amine 99 or N, dinethylformamide, described ether compound is a methyl ethyl ether, ether, positive propyl ether or n-butyl ether, described ester compound are TRI N BUTYL PHOSPHATE, triphenylphosphate, diisobutyl phthalate or dioctyl phthalate (DOP).
8. sulfoacid rare earth catalyst according to claim 4 is characterized in that, described aluminum alkyls is diisobutylaluminium hydride Al (i-Bu)
2H or triisobutyl aluminium Al (i-Bu)
3
9. the preparation method of a sulfoacid rare earth catalyst is characterized in that, comprising:
With the trifluoromethanesulfonic acid rare earth compound, give electronics part and solvent, heating obtains the trifluoromethanesulfonic acid rare earth compounding, described rare earth element is 1: 3～10 with described mol ratio to the electronics part;
Described trifluoromethanesulfonic acid rare earth compounding and aluminum alkyls are mixed, obtain sulfoacid rare earth catalyst, the mol ratio of the rare earth element in described aluminum alkyls and the trifluoromethanesulfonic acid rare earth compounding is 10～60: 1.
10. the preparation method of a polyhutadiene is characterized in that, comprising:
The alkane solution and the sulfoacid rare earth catalyst of divinyl are mixed, react under 0～70 ℃ of condition, obtain polyhutadiene, described sulfoacid rare earth catalyst comprises that aluminum alkyls and molecular formula are Ln (CF
3SO
3)
3XH
2The trifluoromethanesulfonic acid rare earth compounding of OyL, wherein, Ln is a rare earth element, L is to the electronics part, 0＜x≤8,1≤y≤4, the mol ratio of described aluminum alkyls and described Ln is 10～60: 1, described rare earth element is 1.0 * 10 with the molar mass ratio of described divinyl
-5～9.0 * 10
-5Mol: 1g.
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