CN103319544A - Rare earth complex and application method thereof - Google Patents

Rare earth complex and application method thereof Download PDF

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CN103319544A
CN103319544A CN2013102651290A CN201310265129A CN103319544A CN 103319544 A CN103319544 A CN 103319544A CN 2013102651290 A CN2013102651290 A CN 2013102651290A CN 201310265129 A CN201310265129 A CN 201310265129A CN 103319544 A CN103319544 A CN 103319544A
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rare earth
earth compounding
title complex
thf
multiplet
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许卫锋
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Nanjing CEC Panda LCD Technology Co Ltd
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Nanjing CEC Panda LCD Technology Co Ltd
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Abstract

The invention provides a rare earth complex and an application method thereof in preparation of an oriented polymer, wherein the rare earth complex is prepared from a colourless liquid ligand and an organic lithium compound (n-BuLi) by chemical reaction; and the rare earth complex forms a crystal shape. The invention also provides the application method of the rare earth complex. The rare earth complex is prepared from the ligand, and applied to a catalyst of a liquid crystal alignment film. The catalytic performance of the rare earth complex is researched by the proposed methods of six rare earth complexes; the oriented polymer with three-dimensional regularity is widely applied to the fields such as optics, medical treatment and display; and the optimized novel catalyst and reaction condition have more excellent efficiency and orientation of preparing the oriented polymer.

Description

A kind of rare earth compounding and application method thereof
Technical field
The present invention relates to a kind of novel rare-earth title complex and at the application method of preparation orientation polymkeric substance.
Background technology
In the TFT-LCD technology, coat the alignment film on CF substrate and the TFT substrate, play a part control Liquid Crystal Molecules Alignment direction, because the interface between liquid crystal and the alignment film has (Anchoring Strength) in the very strong effect, after impressed voltage was cancelled, the liquid crystal molecule after the change orientation returned to original state against viscoelasticity.Alignment film need to carry out orientation and process the arrangement that could effectively control liquid crystal molecule, and alignment technique mainly contains rubbing manipulation (Rubbing) and non-rubbing manipulation (Non-Rubbing) two large classes.
Traditional TN type liquid crystal reaches the more use rubbing manipulation of method (Rubbing) of certain orientation, TN type liquid crystal adopts the PT(polyimide more, Polyimide) orientation, but this mechanical rubbing manipulation need regularly replace consumptive material, might introduce the impurity effect productive efficiency simultaneously.
VA type liquid crystal adopts PSVA(polymer stabilizing vertical orientation more, Polymer Stabilization Vertical Alignment) technology and UV2A(UV light vertical orientation, UV vertical Alignment) two kinds of methods (non-rubbing manipulation orientation) of controlling liquid crystal aligning of technology.
The PSVA technology is the VA panel technology that Youda, Samsung etc. develop jointly, to use the reaction of open loop closed-loop type, the PSVA technology is will sneak in the liquid crystal photaesthesia or heat sensitive prepolymer in advance, make under the liquid crystal molecules tilt state applying voltage, polymerization single polymerization monomer is stored the polymer orientation supporting technology of the vergence direction of liquid crystal molecule thus.But there is some problems in the PSVA technology, because the remaining monomer of polyreaction is sneaked in the liquid crystal material, this and similar small molecules counter plate of liquid crystal integral body has certain impact.
UV 2The A technology is to utilize alignment films to control the method for tilted alignment, UV 2The A technology is that it has high contrast and shorter reaction times by the technology of Japanese Sharp company exploitation.UV 2What A used is light orientation method, by changing the radiation modality of light, is prepared into accurate orientation segmenting structure, and this difficult static and the impurity of producing of method of processing alignment films in contactless mode is a kind of good method; UV 2The A technology is to use UV rayed styracin lipid aggregate precursor, and [2+2] type ring closure reaction occurs, and forms anisotropy.Be that thermostability is inadequate but the problem that this method is larger is polymkeric substance, reduce the shortcomings such as orientation stability or thermostability or liquid crystal aligning be abundant not, and the cost of this aligning film material be more many than common alignment film costliness.
Summary of the invention
The present invention relates to a kind of catalyst that utilizes and gather simple monomer, make and originally do not have that the material of orientation has the rare earth compounding of certain regioselectivity and at the application method of preparation orientation polymkeric substance.
The invention provides a kind of rare earth compounding, this rare earth compounding is made by the part that is the colourless liquid shape and organolithium compound (n-BuLi) after chemical reaction, and this rare earth compounding is lenticular.
Wherein, described part is (i-Pr) 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3, this part is by 1,3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) and (i-Pr) 3The SiCl after chemical reaction is made.
Wherein, the chemical formula of described rare earth compounding is [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Sm IIILi (THF) 4, it is to be made by described part and samarium trichloride (SmCl3) after chemical reaction.
Wherein, the chemical formula of described rare earth compounding is [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4, it is by described part and Europium trichloride (EuCl 3) after chemical reaction makes.
Wherein, described part is [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4, this part is by 1,3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) and Europium trichloride (EuCl 3) after chemical reaction makes.
Wherein, the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Eu III(THF)] 2Cl, it is by described part and Europium trichloride (EuCl 3) after chemical reaction makes.
Wherein, the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Sm III(THF) Cl] 22LiCl, it is by described part and samarium trichloride (SmCl 3) after chemical reaction makes.
Wherein, the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Yb III(THF) Cl] 22LiCl, it is by described part and Ytterbium trichloride (YbCl 3) after chemical reaction makes.
Wherein, the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Y III(THF) Cl] 22LiCl, it is by described part and Yttrium trichloride (YCl 3) after chemical reaction makes.
The present invention also provides a kind of application method of rare earth compounding, and this rare earth compounding is made by part, and this rare earth compounding is used for the catalyzer of liquid crystal orienting film.
The present invention passes through the method for six kinds of rare earth compoundings of proposition, and it has been carried out catalytic performance research: the orientation polymkeric substance with three-dimensional regularity has in optics, medical treatment, demonstration field widely to be used; And efficient and orientation that the new catalyst after optimizing and reaction conditions have more excellent preparation orientation polymkeric substance.
Description of drawings
Fig. 1 is the crystalline structure schematic diagram of the first polymkeric substance.
Embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate the present invention, should understand these embodiment only is used for explanation the present invention and is not used in and limits the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
The present invention is a kind of rare earth compounding for liquid crystal orienting film, and this rare earth compounding makes original material of not having orientation have certain regioselectivity, forms the orientation film.
All experimental implementation of the present invention all in the uncommon Rec of the Schlenk(of standard technology, are called again the biexhaust pipe operative technique) carry out under the technology, adopt under the dry pure argon shield and carry out, experiment reaction needed solvent and various chemical substance.Wherein, solvent is the THF(tetrahydrofuran (THF), Tetrahydrofuran); Chemical substance: toluene, normal hexane, ether, DME(dme, be called for short methyl ether, Dimethyl ether) etc. all under argon shield with sodium silk, benzophenone backflow purple or red-purple, distillation is used immediately; Chemical substance: the MMA(organolanthanide complexes), it uses CaH 2Underpressure distillation after dry; Other reagent is analytical pure except indicating especially; Anhydrous LnCl 3(Ln=Sm, Eu, Yb, Y) [109], n-BuLi [110]Press the literature method preparation, other reagent is analytical pure except indicating especially, directly use.
The address of above-mentioned literature method is: [109]. (a) William J.Evans, Laura A.Hughes, and Timothy P.Hanusa, Synthesis and crystallographic characterization of an unsolvated, monomeric samarium bis (pentamethylcyclopentadienyl) organolanthanide complex, (C 5Me 5) 2Sm, J.Am.Chem.Soc.1984,106,4270 – 4272. (b) William J.Evans, Laura A.Hughes, and Timothy P.Hanusa, Synthesis and x-ray crystal structure of bis (pentamethylcyclopentadienyl) complexes of samarium and europium:(C 5Me 5) 2Sm and (C 5Me 5) 2Eu, Organometallics1986,5,1285-1291.; [110]. (a) Evans, W.J.; Nyce, G.W.; Clark, R.D.; , Angew.Chem.Int.Ed.Engl.1999,38,1801. (b) Evans, W.J.; Davis, B.L.; Ziller, J.W.Synthesis and Structure of Tris (alkyl-and silyl-tetramethylcyclopentadienyl) Complexes of Lanthanum, Inorg.Chem.2001,40,6341-6348..
The IR(infrared rays) with BIO-RAD FTS-40 type infrared spectrometer, adopts KCl compressing tablet and fluorocarbon oil to stick with paste the method sample preparation, measure immediately sweep limit 400-4000cm at infrared spectrometer -1Measure; Carbon, hydrogen, nitrogen analysis adopt combustion method, measure at Vario EL III carbon, hydrogen, nitrogen elemental analyser; Fusing point test is enclosed in title complex in the kapillary of anhydrous and oxygen-free processing, adopts the airbath heating; The kapillary sealed-tube method is adopted in crystal structure determination.Select suitable crystal and pack in the kapillary, collect data under the tube sealing, low temperature; GPC Waters-2414 gel permeation chromatograph under 30 ℃, is made moving phase with THF and is measured; HNMR spectrum Bruker AV-300 nmr determination.
Below be the synthetic method of part of the present invention, the present invention has two kinds of parts, and called after first cooperates and the second cooperation respectively.
The described first chemical formula that cooperates is: (i-Pr) 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3Synthetic, the preparation method of this first part is in the present embodiment: under-78 ℃, at first get 1 of the 0.50ml that newly is steamed out and 5.95mmol, 3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) be placed among the 50.0mL solvent THF; Slowly drip again the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 6.8mL and 11.9mmol) of 1.75M; After dropwising, the temperature of mixture slowly rises to room temperature and continues and stirred 12h(hour); Then reaction mixture is chilled to 0 ℃ again; Slowly drip again the 2.5ml newly be steamed out and (i-Pr) of 11.9mmol 3SiCl; After dropwising, mixture temperature slowly rises to again room temperature and continues and stirred 12h(hour) after, vacuum is taken out desolventizing; Then use 20mL * 3 hexanes (C6H14) to extract three times, united extraction liquid, 85 ℃/2mmHg of underpressure distillation obtains the colourless liquid of 1.726g, and this colourless liquid is exactly the first cooperation (i-Pr) of the present invention 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3, this first output that cooperates is 75%.
By the first part that above-mentioned experiment obtains, it is verified the first result who cooperates who obtains under nucleus magnetic hydrogen spectrum HNMR condition, the solvent employing deuterochloroform solvent C DCl of checking 3, in the present embodiment, nucleus magnetic hydrogen spectrum HNMR conditional parameter is: hydrogen peak shift (ppm) 2.84(quartet, 4 hydrogen), 1.57) (multiplet, 2 hydrogen), 1.27(multiplet, 2 hydrogen), 1.10(bimodal, 32 hydrogen), 0.26(multiplet, 6 hydrogen).
The described second chemical formula that cooperates is: Me 3SiNHCH 2CH 2CH 2NHSiMe 3Synthetic, the preparation method of this Ligands is in the present embodiment: under-78 ℃, at first get 1 of the 0.84ml that newly is steamed out and 9.98mmol, 3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) be placed among the 50.0mL solvent THF; Slowly drip again the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 12.2mL and 20.0mmol) of 1.64M; After dropwising, the temperature of mixture slowly rises to room temperature and continues and stirred 12h(hour); Then reaction mixture is chilled to 0 ℃ again; Slowly drip again the 2.8ml newly be steamed out and the Me of 21.9mmol 3SiCl; After dropwising, mixture temperature slowly rises to again room temperature and continues and stirred 12h(hour) after, vacuum is taken out desolventizing; Then use 20mL * 3 hexanes (C6H14) to extract three times, united extraction liquid, 52 ℃/2mmHg of underpressure distillation obtains the colourless liquid of 1.747g, and this colourless liquid is exactly the second cooperation Me of the present invention 3SiNHCH 2CH 2CH 2NHSiMe 3, this first output that cooperates is 80%.
By the Ligands that above-mentioned experiment obtains, it is verified the second result who cooperates who obtains under nucleus magnetic hydrogen spectrum HNMR condition, the solvent employing deuterochloroform solvent C DCl of checking 3, in the present embodiment, nucleus magnetic hydrogen spectrum HNMR conditional parameter is: hydrogen peak shift (ppm) 2.72(multiplet, 4 hydrogen), 1.54(multiplet, 2 hydrogen), 0.98(is unimodal, 2 hydrogen) and, 0.02(is bimodal, 16 hydrogen).
The above-mentioned preparation method that two kinds of parts of the present invention are described, because it is different to add solvent: that the first part adds is (i-Pr) 3SiCl is therefore the first part that obtains is (i-Pr) 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3That Ligands adds is Me 3SiCl is therefore the Ligands that obtains is Me 3SiNHCH 2CH 2CH 2NHSiMe 3
I-Pr is sec.-propyl, and Me is methyl, and the difference of the first part and Ligands is that the collective that adds is different, but i-Pr and Me all belong to organic matrix, and the first part and Ligands have public technical characterictic 1,3-propylene diamine (NH 2CH 2CH 2CH 2NH 2), therefore have unicity between the first part and the Ligands, simultaneously in the present invention application.
Rare earth compounding of the present invention has six kinds, difference called after the first title complex, the second title complex, the 3rd title complex, the 4th title complex, the 5th title complex, the 6th title complex, wherein, the first title complex and the second title complex are made by the first part, the the 3rd to the 6th title complex all has Ligands to make, and below is these six kinds of preparation methods that are engaged in the present embodiment.
The chemical formula of described the first title complex is: [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Sm IIILi (THF) 4Synthetic, the preparation method of this first title complex is in the present embodiment: under-78 ℃, at first get the first part (i-Pr) of the 9.57mmol that distills 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 11.0mL and 19.2mmol) that slowly drips again 1.79M obtains (i-Pr) at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSi (i-Pr) 3Then the SmCl that adds 2.46g and 9.57mmol under the logical argon gas 3(samarium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the trivalent rare earth metals samarium complex through concentrated recrystallization with 65% productive rate, and the color of this title complex is orange-yellow rhomboidan, its be exactly the first title complex of the present invention [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Sm IIILi (THF) 4, this first title complex is confirmed its structure such as Fig. 1 through the monocrystalline X-ray diffraction.
Under fusing point 186-188 ℃, with infrared IR absorption peak (Nujol molls, cm -1) the first title complex obtained above is tested, obtain following data: wavelength υ: 3985 multiplet m, 3969 multiplet m, 3441 unimodal s, 3421 unimodal s, 3360 unimodal s, 3333 unimodal s, 3020 unimodal s, 2959 unimodal s, 2195 broad peak w, 2040 broad peak w, 1609 unimodal s, 1512 multiplet m, 1466 multiplet m, 1400 broad peak w, 1346 broad peak w, 1254 unimodal s, 1219 broad peak w, 1057 multiplet m, 945 multiplet m, 887 multiplet m, 841 unimodal s, 725m, 613 unimodal s, 548 unimodal s, 520 unimodal s.Can confirm the first title complex that above-mentioned experiment obtains by above data.
The chemical formula of described the second title complex is: [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4Synthetic, the preparation method of this second title complex is in the present embodiment: under-78 ℃, at first get the first part (i-Pr) of the 11.2mmol that distills 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 13.7mL and 22.5mmol) that slowly drips again 1.64M obtains (i-Pr) at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSi (i-Pr) 3Then the EuCl that adds 2.91g and 11.2mmol under the logical argon gas 3(Europium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then with 10mL ice hexane washing solid, vacuum is taken out desolventizing again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the scarlet crystal of trivalent rare earth title complex with 55% productive rate through concentrated recrystallization, this scarlet crystal be exactly the second title complex of the present invention [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4
Above-mentioned two kinds of title complexs that illustrated in six kinds of title complexs of the present invention: the preparation method of the first title complex and the second title complex, the first title complex and the second title complex all be by the first part as raw material, additive is different and produce different title complexs in the first part again: the first title complex adds SmCl in the preparation process in the first part 3(samarium trichloride), the first title complex that obtains are [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Sm IIILi (THF) 4The second title complex adds EuCl in the preparation process in the first part 3(Europium trichloride), the second title complex that obtains are [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4
Owing to having introduced Sm in the above-mentioned document [109] and Eu all belongs to rare earth element; therefore the first title complex and the second title complex be different at rare earth element just; has public technical characterictic the first part between them, therefore the simultaneously in the present invention protection of the first title complex and the second title complex.
The chemical formula of described the 3rd title complex is: [Me 3SiNCH 2CH 2CH 2NSiMe 3Eu III(THF)] 2Cl's is synthetic, and the preparation method of the 3rd title complex is in the present embodiment: under-78 ℃, at first get the Ligands Me of the 25.5mmol that distills 3SiNHCH 2CH 2CH 2NHSiMe 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 66.8mL and 51.0mmol) that slowly drips again 0.76M obtains Me at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSiMe 3Then the EuCl that adds 6.57g and 25.5mmol under the logical argon gas 3(Europium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then with 10mL ice hexane washing solid, vacuum is taken out desolventizing again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the wine-colored crystal of trivalent rare earth title complex through concentrated recrystallization with 66% productive rate, and this wine-colored crystal is exactly the 3rd title complex [Me of the present invention 3SiNCH 2CH 2CH 2NSiMe 3Eu III(THF)] 2Cl.
Under fusing point 121-122 ℃, with infrared IR absorption peak (Nujol molls, cm -1) the 3rd title complex obtained above is tested, obtain following data: wavelength υ: 2939 unimodal s, 2901 unimodal s, 2866 unimodal s, 2187 broad peak w, 1593 unimodal s, 1512 multiplet m, 1477 multiplet m, 1442 multiplet m, 1396 multiplet m, 1350 multiplet m, 1250 unimodal s, 1053 unimodal s, 903 unimodal s, 829 unimodal s, 798 multiplet m, 748 multiplet m, 725 multiplet m, 659 multiplet m, 590 multiplet m, 528 multiplet m, 513 multiplet m.Can confirm the 3rd title complex that above-mentioned experiment obtains by above data.
To the ultimate analysis (calculating with content %) of the 3rd title complex, the ultimate analysis theoretical value of the 3rd title complex is: C content 32.87%, H content 6.58%, N content 5.90%; The ultimate analysis measured value is: C content 34.68%, H content 7.09%, N content 6.56%.Ultimate analysis measured value and the theoretical value of the 3rd title complex are more or less the same Pass Test.
The chemical formula of described the 4th title complex is: [Me 3SiNCH 2CH 2CH 2NSiMe 3Sm III(THF) Cl] 22LiCl's is synthetic, and the preparation method of the 4th title complex is in the present embodiment: under-78 ℃, at first get the Ligands Me of the 7.47mmol that distills 3SiNHCH 2CH 2CH 2NHSiMe 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 10.8mL and 14.94mmol) that slowly drips again 1.39M obtains Me at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSiMe 3Then the SmCl that adds 1.92g and 7.47mmol under the logical argon gas 3(samarium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then with 10mL ice hexane washing solid, vacuum is taken out desolventizing again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the orange-yellow crystal of trivalent rare earth title complex through concentrated recrystallization with 60% productive rate, and this orange-yellow crystal is exactly the 4th title complex [Me of the present invention 3SiNCH 2CH 2CH 2NSiMe 3Sm III(THF) Cl] 22LiCl.
Under fusing point 158-160 ℃, with infrared IR absorption peak (Nujol molls, cm -1) the 4th title complex obtained above is tested, obtain following data: wavelength υ: 3279 unimodal s, 3259 unimodal s, 3236 unimodal s, 3205 unimodal s, 3132 unimodal s, 3066 unimodal s, 3039 unimodal s, 2955 unimodal s, 1609 unimodal s, 1512 multiplet m, 1469 multiplet m, 1396w, 1346w, 1254s, 1057 multiplet m, 888 multiplet m, 841 unimodal s, 748 multiplet m, 555 multiplet m, 536 multiplet m, 501 multiplet m.Can confirm the 4th title complex that above-mentioned experiment obtains by above data.
To the ultimate analysis (calculating with content %) of the 4th title complex, the ultimate analysis theoretical value of the 4th title complex is: C content 30.27%, H content 6.06%, N content 5.43%; The ultimate analysis measured value is: C content 30.33%, H content 6.31%, N content 5.32%.Ultimate analysis measured value and the theoretical value of the 4th title complex are more or less the same Pass Test.
The chemical formula of described the 5th title complex is: [Me 3SiNCH 2CH 2CH 2NSiMe 3Yb III(THF) Cl] 22LiCl's is synthetic, and the preparation method of the 5th title complex is in the present embodiment: under-78 ℃, at first get the Ligands Me of the 10.9mmol that distills 3SiNHCH 2CH 2CH 2NHSiMe 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 29.0mL and 21.8mmol) that slowly drips again 0.76M obtains Me at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSiMe 3Then add 3.03 and the YbCl of 10.9mmol under the logical argon gas 3(Ytterbium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then with 10mL ice hexane washing solid, vacuum is taken out desolventizing again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the crystal of the orange red rhombus of trivalent rare earth title complex with 56% productive rate through concentrated recrystallization, and the crystal of this orange red rhombus is exactly the 5th title complex [Me of the present invention 3SiNCH 2CH 2CH 2NSiMe 3Yb III(THF) Cl] 22LiCl.
Under fusing point 114-116 ℃, with infrared IR absorption peak (Nujol molls, cm -1) the 5th title complex obtained above is tested, obtain following data: wavelength υ: 3379 unimodal s, 3364 unimodal s, 3317 unimodal s, 3298 unimodal s, 2951 unimodal s, 2384w, 2338w, 1913w, 1856w, 1663 multiplet m, 1582 multiplet m, 1512 multiplet m, 1443 multiplet m, 1381 multiplet m, 1250 unimodal s, 1126 unimodal s, 1088 multiplet m, 968 unimodal s, 898 multiplet m, 833 unimodal s, 748 multiplet m, 671 multiplet m.Can confirm the 5th title complex that above-mentioned experiment obtains by above data.
To the ultimate analysis (calculating with content %) of the 5th title complex, the ultimate analysis theoretical value of the 5th title complex is: C content 29.00%, H content 5.80%, N content 5.20%; The ultimate analysis measured value is: C content 29.71%, H content 5.34%, N content 5.26%.Ultimate analysis measured value and the theoretical value of the 5th title complex are more or less the same Pass Test.
The chemical formula of described the 6th title complex is: [Me 3SiNCH 2CH 2CH 2NSiMe 3Y III(THF) Cl] 22LiCl's is synthetic, and the preparation method of the 6th title complex is in the present embodiment: under-78 ℃, at first get the Ligands Me of the 11.3mmol that distills 3SiNHCH 2CH 2CH 2NHSiMe 3Be placed among the 50.0mL solvent THF; Then the n-BuLi (n-BuLi is a kind of organolithium compound, and it is preferably taken from, and oneself makes, and quantity is 12.8mL and 22.8mmol) that slowly drips again 1.76M obtains Me at-78 ℃ of lower reaction 12h 3SiNLiCH 2CH 2CH 2NLiSiMe 3Then add 2.21 and the YCl of 11.3mmol under the logical argon gas 3(Yttrium trichloride) back flow reaction 24 hours, vacuum is taken out desolventizing to solid again; Then with 10mL ice hexane washing solid, vacuum is taken out desolventizing again; Then use 20mL * 3 hexane extraction three times, united extraction liquid obtains the lurid crystal of trivalent rare earth title complex through concentrated recrystallization with 58% productive rate, and this lurid crystal is exactly the 6th title complex [Me of the present invention 3SiNCH 2CH 2CH 2NSiMe 3Y III(THF) Cl] 22LiCl.
Under fusing point 164-166 ℃, with infrared IR absorption peak (Nujol molls, cm -1) the 6th title complex obtained above is tested, obtain following data: wavelength υ: 3491 unimodal s, 3383 unimodal s, 3344 unimodal s, 3275 unimodal s, 3194 unimodal s, 3120 unimodal s, 3036 unimodal s, 2963 unimodal s, 2924 unimodal s, 2851 unimodal s, 2766 multiplet m, 2724 multiplet m, 2087 broad peak w, 1643 unimodal s, 1585 unimodal s, 1527 unimodal s, 1500 unimodal s, 1443 multiplet m, 1392 multiplet m, 1330 multiplet m, 1261s, 1222 broad peak w, 999 multiplet m, 952 multiplet m, 937 multiplet m, 822s, 779 multiplet m, 714 multiplet m, 694 multiplet m, 656 multiplet m, 575 multiplet m, 509 multiplet m; By nucleus magnetic hydrogen spectrum HNMR conditional parameter be: hydrogen peak shift (ppm) 3.78(broad peak, 8 hydrogen), 2.74(is bimodal, 8 hydrogen), 1.86(is bimodal, 8 hydrogen), 1.49(triplet, 4 hydrogen), 0.07(multiplet, 36 hydrogen).Can confirm the 6th title complex that above-mentioned experiment obtains by above data.
To the ultimate analysis (calculating with content %) of the 6th title complex, the ultimate analysis theoretical value of the 6th title complex is: C content 37.90%, H content 7.59%, N content 6.80%; The ultimate analysis measured value is: C content 38.80%, H content 7.26%, N content 6.75%.Ultimate analysis measured value and the theoretical value of the 6th title complex are more or less the same Pass Test.
The above-mentioned other four kinds of title complexs that illustrated in six kinds of title complexs of the present invention: the preparation method of the 3rd to the 6th title complex, the the 3rd to the 6th title complex all be by Ligands as raw material, additive is different and produce different title complexs in Ligands again: the 3rd title complex adds EuCl in the preparation process in Ligands 3(Europium trichloride), the 3rd title complex that obtains is [Me 3SiNCH 2CH 2CH 2NSiMe 3Eu III(THF)] 2Cl; The 4th title complex adds SmCl in the preparation process in Ligands 3(samarium trichloride), the 4th title complex that obtains is [Me 3SiNCH 2CH 2CH 2NSiMe 3Sm III(THF) Cl] 22LiCl; The 5th title complex adds YbCl in the preparation process in Ligands 3(Ytterbium trichloride), the 5th title complex that obtains is [Me 3SiNCH 2CH 2CH 2NSiMe 3Yb III(THF) Cl] 22LiCl.The 6th title complex adds YCl in the preparation process in Ligands 3(Yttrium trichloride), the 6th title complex that obtains is [Me 3SiNCH 2CH 2CH 2NSiMe 3Y III(THF) Cl] 22LiCl.
All belong to rare earth element owing to having introduced Eu, Sm, Yb, Y in the above-mentioned document [109]; therefore the 3rd to the 6th title complex is the difference at rare earth element; has public technical characterictic Ligands between them; again because have unicity between the first part and the Ligands; therefore also have unicity between the first to the 6th title complex, simultaneously in the present invention protection.
The above-mentioned preparation method who introduces six kinds of title complexs of the present invention, these six kinds of title complexs all are rare earth compoundings, this rare earth compounding is used for the catalyzer of liquid crystal orienting film, has the function that the orientation film is made in catalysis, below is that six kinds of title complexs of the present invention are as the research of catalysis MMA polyreaction.
According to the polymkeric substance of published Chinese patent CN201180007896.0 and CN201180017747.2 analysis liquid crystal orientation, the necessary structural unit of the polymkeric substance of liquid crystal aligning is that following chemical formula is [changing 1]:
Figure BDA00003420759400101
[changing 1]
But when the design polymkeric substance, the necessary monomer of its target product, its chemical formula are [changing 2] and [changing 3]:
Figure BDA00003420759400102
[changing 2]
Figure BDA00003420759400103
[changing 3]
This class monomer is the MMA(methyl methacrylate namely), the MMA(methyl methacrylate) be a kind of organism, its molecular formula is CH 2=C (CH 3) CO 2CH 3It is a kind of colourless liquid, the MMA(methyl methacrylate) methacrylic acid (MAA) and methanol esterification are formed, it is to produce transparent plastics PMMA(polymethylmethacrylate, its molecular formula is: molecular formula: monomer-[CH2C (CH3) (COOCH3)] n-), therefore in the present invention, select MMA as the monomer of polymerization.
The uncommon Rec of Schlenk(technology is used in the polyreaction operation of MMA; claiming again the biexhaust pipe operative technique) technology carries out under the argon shield of anhydrous and oxygen-free; in 50mL Schlenk reaction flask, add a certain amount of catalysts and solvents; the hierarchy of control temperature required and stable after, with the disposable adding of syringe metering, use CaH 2(hydrolith) MMA(methyl methacrylate that processed, new steaming) as monomer, having tested respectively six kinds of rare earth compoundings that the present invention synthesizes as the one-component catalyzer, is that 1:500, monomer and solvent ratio (V/V) are the polyreaction under 1:3, differing temps, the different solvents condition than (mol/mol) at catalyzer and monomer.Reaction stops polyreaction with a certain amount of methyl alcohol after the set time, elimination solution, polymkeric substance 50 ℃ of lower vacuum-dryings to constant weight.
The stereoregular type of polymkeric substance and molecular weight are respectively by nucleus magnetic hydrogen spectrum HNMR (CDCl 3Trichloromethane) and the GPC(gel permeation chromatography, GelPermeationChromatography) determine, research is found, six kinds of rare earth compoundings of the present invention can be used for catalysis MMA polyreaction, in wide temperature range, have very high catalytic activity, and obtain that molecular weight is higher, narrow distribution, the medium polymkeric substance of stereoregular type.
From nucleus magnetic hydrogen spectrum HNMR result, two replace the diamines ylidene ligands is present in the middle of the chain of polymerisate on a small quantity, shows that polymerization may occur by chemical formula [changing 4] process:
Figure BDA00003420759400111
[changing 4]
Because MMA is the monomer of producing PMMA, therefore the stereoregular type of monomer M MA and molecular weight must be studied several unit of the short chain of PMMA.
[changing 5] is the PMMA(polymethylmethacrylate, and its molecular formula is: molecular formula: the chemical formula of several unit of short chain-[CH2C (CH3) is (COOCH3)] n-), and for distinguishing the difference of its configuration: m represents isotactic, rule between r represents:
Figure BDA00003420759400121
[changing 5]
[changing 6] is congruence rule polymeric chemical formula:
Figure BDA00003420759400122
[changing 6]
[changing 7] is the chemical formula of full syndiotactic polymerization:
Figure BDA00003420759400123
[changing 7]
Concrete experimental data is shown in following table one: each data parameters of table one is respectively: the solvent of table one is 3:1 with monomer than (V/V), solvent is selected the THF(tetrahydrofuran (THF), Tetrahydrofuran), Tolu.(toluene) and the DME(glycol dimethyl ether) three kinds of solvents, catalyzer is 1:500 with monomer than (mol/mol), active unit is: gpMMA/molcat.h, catalyst A in the middle of the table one is sample reference data, and concrete table one is as follows:
Six kinds of catalyzed by rare-earth complex MMA of table one polymerization activity
Figure BDA00003420759400131
According to the data of table one, draw to draw a conclusion:
The 3rd complex-catalyzed MMA has very high transformation efficiency under the conditions such as suitable temperature, solvent, activity (can reach 10 7GpMMA/molcat.h) and narrower molecular weight distribution, has potential industrial value.
The Mw/Mn value that the first complex-catalyzed MMA obtains under conditions suitable has potential industrial value near ideal value 1.00.
Rule content is relatively high in the middle of polar solvent THF, DME, polymerization in polar solvent THF has good activity for the 3rd title complex, and part is active high, and number average and matter average molecular weight are all very high, and the molecular weight distribution of product is very narrow, shows the using value that this compounds is potential.
Also all large with 50% as rule content between the polymkeric substance that obtains among the THF of the 3rd to the 6th title complex of different metal identical ligands and the DME, isotactic content shows that more than 59% this series part has regular aggregate performance excellence aspect the controlled catalyzed polymerization in the toluene solution of the 4th to the 6th title complex.
Solvent not only affects the activity of catalyzer, affect simultaneously the tacticity of polymer P MMA, isotactic content is higher under non-polar solvent toluene condition, and first, second title complex and the 4th to the 6th title complex are better than contrasting the result of sample A all above 59%.
Above-mentioned studies show that, six kinds of novel rare-earth title complexs of the present invention have certain orientation polymerization effect to MMA, if be optimized for front aggressiveness, cooperate this novel title complex of direct current guiding polymerization to have certain industrial applications again.
The present invention passes through the method for six kinds of rare earth compoundings of proposition, and it has been carried out catalytic performance research: the orientation polymkeric substance with three-dimensional regularity has in optics, medical treatment, demonstration field widely to be used; And efficient and orientation that the new catalyst after optimizing and reaction conditions have more excellent preparation orientation polymkeric substance.

Claims (10)

1. rare earth compounding, it is characterized in that: this rare earth compounding is made by the part that is the colourless liquid shape and organolithium compound (n-BuLi) after chemical reaction, and this rare earth compounding is lenticular.
2. rare earth compounding according to claim 1 is characterized in that: described part is (i-Pr) 3SiNHCH 2CH 2CH 2NHSi (i-Pr) 3, this part is by 1,3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) and (i-Pr) 3The SiCl after chemical reaction is made.
3. rare earth compounding according to claim 2 is characterized in that: the chemical formula of described rare earth compounding is for [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Sm IIILi (THF) 4, it is to be made by described part and samarium trichloride (SmCl3) after chemical reaction.
4. rare earth compounding according to claim 2 is characterized in that: the chemical formula of described rare earth compounding is for [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4, it is by described part and Europium trichloride (EuCl 3) after chemical reaction makes.
5. rare earth compounding according to claim 1 is characterized in that: described part is for [(i-Pr) 3SiNCH 2CH 2CH 2NSi (i-Pr) 3] 2Eu IIILi (THF) 4, this part is by 1,3-propylene diamine (NH 2CH 2CH 2CH 2NH 2) and Europium trichloride (EuCl 3) after chemical reaction makes.
6. rare earth compounding according to claim 5, it is characterized in that: the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Eu III(THF)] 2Cl, it is by described part and Europium trichloride (EuCl 3) after chemical reaction makes.
7. rare earth compounding according to claim 5, it is characterized in that: the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Sm III(THF) Cl] 22LiCl, it is by described part and samarium trichloride (SmCl 3) after chemical reaction makes.
8. rare earth compounding according to claim 5, it is characterized in that: the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Yb III(THF) Cl] 22LiCl, it is by described part and Ytterbium trichloride (YbCl 3) after chemical reaction makes.
9. rare earth compounding according to claim 5, it is characterized in that: the chemical formula of described rare earth compounding is [Me 3SiNCH 2CH 2CH 2NSiMe 3Y III(THF) Cl] 22LiCl, it is by described part and Yttrium trichloride (YCl 3) after chemical reaction makes.
10. the application method of the described a kind of rare earth compounding of claim 1-9, it is characterized in that: this rare earth compounding is made by part, and this rare earth compounding is used for the catalyzer of liquid crystal orienting film.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015078789A1 (en) * 2013-11-26 2015-06-04 Wacker Chemie Ag Silylated cyclic phosphonamides
CN105899522A (en) * 2013-11-26 2016-08-24 瓦克化学股份公司 Silylated cyclic phosphonamides
CN109021981A (en) * 2018-06-29 2018-12-18 徐州工程学院 A kind of bonding type fluorescent rare earth Liquid Crystalline Ionomer and preparation method thereof

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