CN104530392A - Preparation method for polylactide - Google Patents
Preparation method for polylactide Download PDFInfo
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- CN104530392A CN104530392A CN201510003230.8A CN201510003230A CN104530392A CN 104530392 A CN104530392 A CN 104530392A CN 201510003230 A CN201510003230 A CN 201510003230A CN 104530392 A CN104530392 A CN 104530392A
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Abstract
The intention discloses a preparation method for polylactide. The preparation method for the polylactide comprises the steps of mixing a catalyst, an organic solvent and lactide, carrying out reaction of ring-opening polymerization in the anhydrous and anaerobic condition and under the protection of inert gas, and obtaining the polyactide through processing reactants after the reaction, wherein the catalyst is amino aniline lithium compounds. According to the preparation method for the polylactide, the amino aniline lithium compounds are used as the catalyst, the reaction controllability is good, the condition is mild, the reaction rate is high, the polymerization reaction can be produced without adding alcohol catalyst promoter, the catalytic activity is high, the obtained polylacide molecular weight is controllable, the yield is high and the metal remain is little. In addition, the technology of the polymerization reaction is simple, common solution polymerization method can be adopted, through controlling the polymerization reaction conditions, molecular weight of the polymer can be regulated and controlled, the selectivity is wide, the molecular weight distribution of the obtained polymer is narrow, the physicochemical property is good, and the requirements of the market can be met.
Description
Technical field
The present invention relates to a kind of amido anilino lithium compound and preparation method thereof, also relate to the method using this amido anilino lithium compound as catalyst preparing polylactide.
Background technology
Take oil as the life that the birth of the macromolecular material of raw material has changed us, each corner of diversified high performance polymer material our daily life of ubiquity, unprecedented convenience is brought to our life, but be alarmingly, under the background of Global Oil growing tension, the fast development relying on the macromolecular material of petroleum is subject to severely restricts.And macromolecule polymeric material is difficult to degraded, and a large amount of macromolecule polymeric material wastes accumulates in for a long time in actual life and also increases the weight of gradually the pollution that environment for human survival causes.Conventional polymer material faces two hang-ups of energy dilemma and environmental pollution, finds the renewable resources replacing oil, and the novel material of development environment friendly, biodegradation type becomes the trend of following macromolecule polymeric material development.
Polylactone is the macromolecular material of the most noticeable environmental type as the high polymer of biodegradable.In natural living environment, discarded polylactone material can be resolved into water and carbonic acid gas thoroughly by the microorganism in soil, environmental protection and renewable.Because polylactone is nontoxic, nonirritant, and has good biocompatibility, be therefore widely used in medical science and field of Environment Protection, such as operating sutures, packaging, drug controlled release and tissue engineering bracket etc.The performance that the excellent biocompatibility of polylactone, biological degradability and Sustainable development utilize, makes it become the promising macromolecular material of 21 century most.
Mostly polylactone is by its corresponding cyclic lactone ring-opening polymerization and obtains, and polyreaction needs to carry out in the presence of a catalyst.Mostly catalyzer conventional is at present the title complex that part and metal are formed, and the metal in catalyzer comprises magnesium, calcium, germanium, tin, aluminium, zinc, iron, titanium, zirconium, group of the lanthanides etc.The selection of catalyzer is all very crucial for the performance of the speed of ring-opening polymerization, products obtained therefrom, therefore studies the good catalyzer of new performance very necessary.
Summary of the invention
The invention provides a kind of preparation method of polylactide, the method is simple to operate, and with amido anilino lithium compound for catalyzer, speed of reaction is fast, and mild condition, products therefrom productive rate is high, narrow molecular weight distribution, molecular weight controllability are good.
Technical solution of the present invention is as follows:
A kind of amido anilino lithium compound, shown in the following formula I of its structural formula, in formula, Ar is the aryl replaced, and is preferably 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl;
。
In above-claimed cpd, gained compound is simple and easy to get, as can be seen from structural formula, the lithium be connected with a part and another part form bridge crosslinking structure, like this carrying out coordination insertion as being more conducive to monomer during catalyzer, catalytic effect is better, is not having also to carry out polyreaction fast under alcohol auxiliary agent.
This amido anilino lithium compound preparation method comprise the following steps: amido anilino part is added in organic solvent, then-10 ~ 30
oadd lithium alkylide under C, make nature rise to room temperature after adding and react, filter after reaction, wash, obtain amido anilino lithium compound.
The equation that amido anilino part and lithium alkylide react is as follows, and wherein the structural formula of amido anilino part is such as formula shown in A, and Ar is the aryl replaced, and is preferably 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl:
In above-mentioned preparation method, amido anilino part used has relevant report in the prior art, such as, describe the synthetic method of this part in patent ZL201210184308.7, such as document (Gao Aihong again, the synthesis of novel aluminum, zinc, chromium metal complexes, sign and catalytic Quality Research, China's Ph.D. Dissertation full-text database) in also disclose the synthetic method of this part, be not described in detail in this.
In above-mentioned preparation method, described lithium alkylide is preferably lithium methide or n-Butyl Lithium.
In above-mentioned preparation method, mol ratio 1:1 ~ 1.3 of amido anilino part and lithium alkylide, preferred 1:1 ~ 1.05.
In above-mentioned preparation method, described organic solvent is one or both in hexane, toluene and hexanaphthene, is preferably hexane or hexanaphthene.
In above-mentioned preparation method, consumption of organic solvent is 5 ~ 40 times of reaction raw materials (part and lithium alkylide) total mass.
In above-mentioned preparation method, react and carry out under protection of inert gas.
In above-mentioned preparation method, lithium alkylide is preferably-10 ~ 0
oadd under C in the mixture of amido anilino part and organic solvent.
In above-mentioned preparation method, part and lithium alkylide at room temperature react 1 ~ 12 hour, preferably 3 ~ 6 hours.
In above-mentioned method for preparing catalyst, washing solvent for use is preferably hexane.
Above-mentioned gained amido anilino lithium compound can be used as the catalyzer that polylactide is prepared in rac-Lactide ring-opening polymerization, and the structural formula of described rac-Lactide is such as formula shown in (III):
。
The preparation method of polylactide specifically comprises the following steps: amido anilino lithium compound catalyzer, organic solvent, alcohol promotor (if any) and rac-Lactide are mixed; under anhydrous and oxygen-free and protection of inert gas, carry out ring-opening polymerization, after reaction, reactant is carried out processing to obtain polylactide.
In above-mentioned ring-opening polymerization, the mol ratio of rac-Lactide and amido anilino Al catalysts is 30 ~ 2000:1.
In aforesaid method, reacting organic solvent used is toluene or tetrahydrofuran (THF), preferred toluene.
In aforesaid method, polymeric reaction temperature is 20 ~ 130 DEG C.
In aforesaid method, polymerization reaction time can be selected within the scope of 1-1440 minute.
In aforesaid method, alcohol promotor is benzylalcohol or Virahol.
In aforesaid method, when using alcohol promotor, the mol ratio of alcohol promotor and catalyzer is 1 ~ 3:1.
In aforesaid method, add water termination reaction after the process carried out reactant refers to reaction, with alcohol settling, for several times, ambient temperature in vacuum is dry, obtains polylactide in washing.
The present invention carries out rac-Lactide ring-opening polymerization using amido anilino lithium compound as catalyzer, and the polylactide narrow molecular weight distribution be obtained by reacting, the molecular weight obtaining product is controlled, and productive rate is high, and metal residual is few.
Amido anilino lithium compound of the present invention is high as catalytic activity during ring-opening polymerization catalyzer, when general metal complexes is as catalyzer, all need in the high catalytic activity of the auxiliary lower competence exertion of alcohol promotor, but catalyzer of the present invention still can have very high catalytic activity in case not having alcohol promotor to deposit, can not affect the carrying out of ring-opening polymerization, the polymkeric substance obtained is the polymkeric substance not having end-blocking.Certainly, catalyzer of the present invention also can alcohol promotor exist under carry out catalyzed ring opening polymerization, now gained product with do not add the structure that alcohol promotor is in a ratio of end-blocking (one end is ether end).
Amido anilino lithium compound method for preparing catalyst of the present invention is simple, cost is low, product yield is high, catalyst structure change is various, catalytic activity is high, safety non-toxic, the ring-opening polymerization of the efficient catalyzing lactone of energy and lactide, can be widely used in cyclic lactone ring-opening polymerization, be a kind of very good catalyzer.
Ring rac-Lactide of the present invention is obtained by rac-Lactide ring-opening polymerization, during preparation with amido anilino lithium compound for catalyzer, reaction controllability is good, mild condition, speed of reaction is fast, do not need to add alcohol promotor and get final product polymerization reaction take place, catalytic activity is high, and the polylactide molecular weight obtained is controlled, productive rate is high, metal residual is few.In addition, polymerization technology of the present invention is simple, can adopt common solution polymerization process, by the control of polymeric reaction condition, can regulate and control the molecular weight of polymkeric substance, selectivity is wide, and the molecular weight distribution obtained is narrow, there is excellent physicochemical property, the needs in market can be met.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of embodiment 3 products obtained therefrom.
Embodiment
Further illustrate the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
In following embodiment, amido anilino part used obtains according to existing method, does not repeat them here.
prepare amido aniline lithium compound (I)
Amido aniline lithium compound reacts by part and lithium alkylide the title complex generated, and the structural formula of its part, as shown in the formula shown in A, is illustrated to the compound that different ligands obtains below.
embodiment 1
Ligand structure formula used is as above formula (A), wherein Ar is 4-aminomethyl phenyl, reaction process is: in a nitrogen atmosphere, part 0.51 g is dissolved in the dry normal hexane of 10 mL, at-10 DEG C, add the n-Butyl Lithium of equimolar amount, be slowly raised to room temperature reaction 3 hours, filter and use dry normal hexane filter wash cake, collect also drying and be weighed as 0.49 g solid, productive rate 94%.
Products therefrom nuclear-magnetism information is as follows, and as can be seen from nuclear-magnetism information, Ar is that the lithium compound of 4-aminomethyl phenyl synthesizes successfully.
1H NMR (400 MHz, CDCl
3)
δ7.40 (d,
J= 7.5 Hz, 2 H, Ph-
H), 7.24–6.91 (m, 10 H, Ph-
H), 6.62 (d,
J= 7.6 Hz, 2 H, Ph-
H), 4.40 (s, 4H, C
H 2N), 2.72 (s, 12 H, NC
H 3), 2.20 (s, 6 H, C
H 3).
13C NMR (100 MHz, CDCl
3)
δ152.45, 146.61, 134.27, 129.81, 128.23, 127.98, 126.66, 124.17, 116.34, 114.34, 48.86, 45.46, 20.40.
embodiment 2
Ligand structure formula used is as above formula (A), wherein Ar is 2,6-3,5-dimethylphenyl, reaction process is: under nitrogen atmosphere, is dissolved in by part 0.47 g in the dry hexanaphthene of 10 mL, adds the n-Butyl Lithium of 1.05 times of molar weights at 0 DEG C, slowly be raised to room temperature reaction 6 hours, filter and use dry normal hexane filter wash cake, to collect and drying is weighed and obtained 0.46 g solid, productive rate 95 %.
Products therefrom nuclear-magnetism information is as follows, and as can be seen from nuclear-magnetism information, Ar is that the lithium compound of 2,6-3,5-dimethylphenyl synthesizes successfully.
1H NMR (400 MHz, CDCl
3)
δ7.42 (dd,
J= 6.2, 1.3 Hz, 2H, Ph-
H), 7.28-7.25 (m, 2H, Ph-
H), 7.17 (dd,
J= 7.0, 1.0 Hz, 2H, Ph-
H), 7.06 (td,
J= 7.4, 1.2 Hz, 2H), 7.00 (d,
J= 7.4 Hz, 4H), 6.83 (t,
J= 7.5 Hz, 2H), 4.17 (s, 4H, NC
H 2Ph), 2.73 (s, 12H, NC
H 3), 2.31 (s, 12H, PhC
H 3).
13C NMR (100 MHz, CDCl
3)
δ152.80, 146.54, 135.08, 129.84, 128.77, 128.09, 123.71, 121.86, 119.72, 49.43, 45.24, 18.41.
embodiment 3
Ligand structure formula used is as above formula (A), wherein Ar is 2,6-diethyl phenyl, reaction process is: under nitrogen atmosphere, is dissolved in 5 mL dry toluene by part 0.34 g, adds the lithium methide of 1.1 times of molar weights at-10 DEG C, be raised to room temperature reaction 1 hour, filter and use dry normal hexane filter wash cake, collecting 0.32 g and drying is weighed to obtain, productive rate 91%.
As shown in Figure 1, nuclear-magnetism information is as follows for the crystalline structure figure of products obtained therefrom, this shows that Ar is that the lithium compound of 2,6-diethyl phenyl synthesizes successfully.
1H NMR (400 MHz, CDCl
3)
δ7.48–7.45 (m, 2H, Ph-
H), 7.29 (dd,
J= 7.8, 1.5 Hz, 2H, Ph-
H), 7.19 (dd,
J= 8.0, 1.1 Hz, 2H, Ph-
H), 7.13 (d,
J= 7.9 Hz, 2H, Ph-
H), 7.09 (m, 4H, Ph-
H), 6.97 (dd,
J= 8.1, 6.9 Hz, 2H, Ph-
H), 4.12 (s, 4H, NC
H 2Ph), 2.73 (s, 12H, NC
H 3), 2.52 (q,
J= 7.5 Hz, 8H, C
H 2CH
3), 1.15 (t,
J= 7.5 Hz, 12H, CH
2C
H 3).
13C NMR (100 MHz, CDCl
3)
δ152.83, 145.45, 136.84, 129.66, 128.09, 126.65, 126.08, 123.87, 122.72, 119.86, 51.29, 45.28, 24.26, 15.10.
embodiment 4
Ligand structure formula used is as above formula (A), wherein Ar is 2,6-diisopropyl phenyl, reaction process is: under nitrogen atmosphere, is dissolved in by part 0.46 g in the dry normal hexane of 20 mL, adds the n-Butyl Lithium of 1.05 times of molar weights at-5 DEG C, be raised to room temperature reaction 12 hours, filter and use dry normal hexane filter wash cake, collecting 0.45 g and drying is weighed to obtain, productive rate 96%.
Products therefrom nuclear-magnetism information is as follows, and as can be seen from nuclear-magnetism information, Ar is that the lithium compound of 2,6-diisopropyl phenyl synthesizes successfully.
1H NMR (400 MHz, CDCl
3)
δ7.48 (d,
J= 7.1 Hz, 2H, Ph-
H), 7.35 – 7.29 (m, 2H, Ph-
H), 7.22 – 7.12 (m, 6H, Ph-
H), 7.06 (m, 4H, Ph-
H), 4.12 (s, 4H, NC
H 2Ph), 3.58–3.36 (m, 4H, C
H(CH
3)
2), 2.78 (s, 12H, NC
H 3), 1.33 (d,
J= 6.5 Hz, 12H CH(C
H 3)
2).
13C NMR (101 MHz, CDCl
3)
δ152.95, 144.22, 137.32, 129.79, 128.25, 127.50, 124.67, 123.72, 123.35, 120.11, 53.11, 45.40, 27.59, 26.51, 25.65.
embodiment 5
Ligand structure formula used is as above formula (A), wherein Ar is 2,6-diethyl phenyl, reaction process is: under nitrogen atmosphere, is dissolved in 5 mL dry toluene by part 0.34 g, adds the lithium methide of 1.05 times of molar weights at-5 DEG C, be raised to room temperature reaction 3 hours, filter and use dry normal hexane filter wash cake, collecting 0.33 g and drying is weighed to obtain, productive rate 96%.
embodiment 6
Ligand structure formula used is as above formula (A), wherein Ar is 2,6-diethyl phenyl, reaction process is: under nitrogen atmosphere, is dissolved in 5 mL dry toluene by part 0.34 g, adds the lithium methide of 1.3 times of molar weights at 30 DEG C, be raised to room temperature reaction 12 hours, filter and use dry normal hexane filter wash cake, collecting 0.30 g and drying is weighed to obtain, productive rate 87%.
prepare polylactide
embodiment 7
Reacting under anhydrous and oxygen-free and protection of inert gas, first adding the rac-Lactide of catalyzer, 30 mL toluene and 20 mmol that 20 μm of ol Ar are 4-aminomethyl phenyl by order in the ampulla after the baking of high pure nitrogen gas washing, being then placed in 80
oin the oil bath of C, react and add a small amount of water termination reaction after 4 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.80 grams, productive rate 97.1%, molecular weight 18.7 ten thousand.
embodiment 8
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-Lactide of catalyzer, 30 mL toluene, 20 μm of ol benzylalcohols and 20 mmol that 20 μm of ol Ar are 4-aminomethyl phenyl by order in the ampulla after the baking of high pure nitrogen gas washing, then 80 are placed in
oin the oil bath of C, react and add a small amount of water termination reaction after 4 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.75 grams, productive rate 95.3%, molecular weight 16.4
Ten thousand
embodiment 9
Reacting under anhydrous and oxygen-free and protection of inert gas, first adding the rac-Lactide of catalyzer, 30 mL toluene and 20 mmol that 20 μm of ol Ar are 4-aminomethyl phenyl by order in the ampulla after the baking of high pure nitrogen gas washing, being then placed in 80
oin the oil bath of C, react and add a small amount of water termination reaction after 8 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.86 grams, productive rate 99.2%, molecular weight 20.1 ten thousand.
embodiment 10
Reacting under anhydrous and oxygen-free and protection of inert gas, first adding the rac-Lactide of catalyzer, 30 mL toluene and 20 mmol that 20 μm of ol Ar are 4-aminomethyl phenyl by order in the ampulla after the baking of high pure nitrogen gas washing, being then placed in 80
oin the oil bath of C, react and add a small amount of water termination reaction after 1 hour, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.64 grams, productive rate 83.2%, molecular weight 12.4 ten thousand.
embodiment 11
React under anhydrous and oxygen-free and protection of inert gas, first adding by order in the ampulla after the baking of high pure nitrogen gas washing that 30 μm of ol Ar are that 2.6-diethylbenzene is catalyst based, the rac-Lactide of 60 mL toluene and 60 mmol, be then placed in 70
oin C oil bath, react and add a small amount of water termination reaction after 12 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 8.53 grams, molecular weight 38.6 ten thousand, yield 98.6%.
embodiment 12
React under anhydrous and oxygen-free and protection of inert gas, first adding by order in the ampulla after the baking of high pure nitrogen gas washing that 1000 μm of ol Ar are that 2.6-dimethyl benzene is catalyst based, the rac-Lactide of 70 mL toluene and 30 mmol, be then placed in 70
oin C oil bath, react and add a small amount of water termination reaction after 1 hour, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 4.16 grams, molecular weight 1.3 ten thousand, yield 96.1%.
embodiment 13
React under anhydrous and oxygen-free and protection of inert gas, first adding by order in the ampulla after the baking of high pure nitrogen gas washing that 20 μm of ol Ar are that 2.6-diisopropyl benzene is catalyst based, the rac-Lactide of 30 mL toluene and 10 mmol, be then placed in 110
oin C oil bath, react and add a small amount of water termination reaction after 1 hour, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 1.33 grams, molecular weight 10.4 ten thousand, yield 92.1%.
embodiment 14
React under anhydrous and oxygen-free and protection of inert gas; first being that 2.6-dimethyl benzene is catalyst based, the rac-Lactide of 30 mL toluene, 20 μm of ol Virahols and 20 mmol with order adds 10 μm of ol Ar in the ampulla after the baking of high pure nitrogen gas washing, then 50 are placed in
oin C oil bath, react and add a small amount of water termination reaction after 7 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.81 grams, molecular weight 10.4 ten thousand, yield 97.2%.
embodiment 15
React under anhydrous and oxygen-free and protection of inert gas; first by order in the ampulla after the baking of high pure nitrogen gas washing, to add 20 μm of ol Ar be that 2.6-diethylbenzene is catalyst based, the rac-Lactide of 50 mL toluene, 10 μm of ol Virahols and 20 mmol, then 20
oc adds a small amount of water termination reaction after reacting 12 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.57 grams, molecular weight 28.3 ten thousand, yield 89.1%.
embodiment 16
React under anhydrous and oxygen-free and protection of inert gas, first adding by order in the ampulla after the baking of high pure nitrogen gas washing that 20 μm of ol Ar are that 2.6-diethylbenzene is catalyst based, the rac-Lactide of 50 mL toluene and 20 mmol, then 20
oc adds a small amount of water termination reaction after reacting 12 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 2.76 grams, molecular weight 17.9 ten thousand, yield 95.7%.
comparative example
Obtaining Ar according to the method for embodiment 1 in patent 201210184308.7 is 4-aminomethyl phenyl, R
1for methyl, R
2for the Amido aniline group zinc compound of ethyl, structural formula is as follows:
The method identical with embodiment 7 is adopted to prepare polylactide, unlike: catalyzer used is this identical substituent Amido aniline group zinc compound, in 80
oin C oil bath, add a small amount of water termination reaction after reaction is increased to 12 hours, with alcohol settling, washing several, ambient temperature in vacuum is dry, obtains 0.24 gram, molecular weight 1.1 ten thousand, yield 8.2%.As can be seen from the results, this kind of catalyzer increase the reaction times also could not the polyreaction of catalysis rac-Lactide smoothly.
Claims (10)
1. a preparation method for polylactide, is characterized in that comprising the following steps: catalyzer, organic solvent and rac-Lactide are mixed, carry out ring-opening polymerization, carried out processing to obtain polylactide by reactant after reaction under anhydrous and oxygen-free and protection of inert gas; Described catalyzer is amido anilino lithium compound, and shown in the following formula I of its structural formula, in formula, Ar is the aryl replaced;
。
2. preparation method according to claim 1, is characterized in that: in formula I, and Ar is 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl.
3. preparation method according to claim 1 and 2, is characterized in that: method for preparing catalyst is: add in organic solvent, then-10 ~ 30 by amido anilino part
oadd lithium alkylide under C, make nature rise to room temperature after adding and react, filter after reaction, wash, obtain amido anilino lithium compound; The structural formula of described amido anilino part is as shown in the formula shown in A, and wherein Ar is the aryl replaced:
。
4. preparation method according to claim 3, is characterized in that: described lithium alkylide is lithium methide or n-Butyl Lithium; Mol ratio 1:1 ~ 1.3 of amido anilino part and lithium alkylide, preferred 1:1 ~ 1.05.
5. preparation method according to claim 3, is characterized in that: described organic solvent is one or both in hexane, toluene and hexanaphthene; Reaction is carried out under protection of inert gas.
6. preparation method according to claim 3, is characterized in that: lithium alkylide is-10 ~ 0
oadd in the mixture of amido anilino part and organic solvent under C; The room temperature reaction time is 1 ~ 12 hour, preferably 3 ~ 6 hours.
7. preparation method according to claim 1, is characterized in that: rac-Lactide and catalyzer mol ratio be 30 ~ 2000:1.
8. preparation method according to claim 1, is characterized in that: described organic solvent is toluene or tetrahydrofuran (THF); Temperature of reaction is 20 ~ 110 DEG C; Reaction times is 1-1440 minute.
9. the preparation method according to claim 1,7 or 8, is characterized in that: also comprise alcohol promotor, and the mol ratio of alcohol promotor and catalyzer is 0.5 ~ 2:1.
10. preparation method according to claim 9, is characterized in that: described alcohol promotor is benzylalcohol or Virahol.
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| CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
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| CN101139436A (en) * | 2007-10-18 | 2008-03-12 | 吉林大学 | Amine imines zinc catalyst and preparation method and use thereof |
| CN102627758A (en) * | 2012-03-31 | 2012-08-08 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
| CN102675617A (en) * | 2012-06-06 | 2012-09-19 | 济南大学 | N,N-dialkyl aniline-arylamine zinc catalyst and preparation method and application thereof |
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| CN101139436A (en) * | 2007-10-18 | 2008-03-12 | 吉林大学 | Amine imines zinc catalyst and preparation method and use thereof |
| CN102627758A (en) * | 2012-03-31 | 2012-08-08 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
| CN102675617A (en) * | 2012-06-06 | 2012-09-19 | 济南大学 | N,N-dialkyl aniline-arylamine zinc catalyst and preparation method and application thereof |
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| KEFENG LIU ET AL.: "Synthesis, characterization, and catalytic properties of new half-sandwich zirconium(IV) complexes", 《DALTON TRANSACTIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
| CN109456342B (en) * | 2018-11-23 | 2020-12-25 | 山西大学 | 1, 2-addition quinolyl lithium complex and synthesis method and application thereof |
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