CN102643417B - Preparation method and application of phenyl-bridged guanyl binuclear rare-earth metal catalyst - Google Patents
Preparation method and application of phenyl-bridged guanyl binuclear rare-earth metal catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts in chemical industry, and particularly relates to a preparation method and application of a binuclear rare-earth metal catalyst. Two rare-earth metals in a rare-earth complex molecule are respectively chelated with two phenyl-bridged large-steric-hindrance substituent guanyl groups and respectively connected with two aphyl groups at the same time, thereby obtaining the binuclear rare-earth metal catalyst. The catalyst has favorable catalytic polymerization performance for caprolactone and lactide, and especially can implement efficient and controllable polymerization of caprolactone under mild conditions. The polymerization temperature is 0-100 DEG C, the monomer conversion rate is up to 100%, and a high molecular material with controllable molecular weight and narrow molecular weight distribution can be obtained; and as for the caprolactone, the number-average molecular weight and the conversion rate have a linear relationship, and the molecular weight distribution is less than 1.5. The number-average molecular weight of the product can be controlled by controlling the metal center/monomer mol ratio, thereby obtaining high molecular materials with different physicochemical properties. The reaction conditions can be changed to further enhance the zone bit and stereoselectivity of the polymerization reaction.
Description
Technical field
The invention belongs to the chemical catalyst technical field, be specifically related to a kind of preparation method and application thereof of double-core rare-earth metal catalyst.
Background technology
In various macromolecular materials, polylactide, polycaprolactone is a kind of multiple advantageous property that has, the polymkeric substance had a extensive future.Wherein, the polylactide material is owing to having nontoxic and can not cause the character that biological immune repels in organism, at plastic surgery, and organizational engineering, and the controlled fields such as medicine input are widely used.In addition, thus polylactide be called as biodegradable type material and be widely used in daily life owing to easily decomposing in environment.The polymkeric substance of more same other polar monomer also becomes the focus of scientist's concern because having good biological property, as caprolactone, and propiolactone etc.This base polymer is mainly to utilize metallic compound catalysis polar monomer to carry out ring-opening polymerization to obtain.Therefore the synthetic metal catalyst with different three-dimensional arrangements and electronic effect becomes the focus that everybody pays close attention to.Some metals comprise aluminium, calcium, the title complex of the preparation of metals such as zinc, character owing to having potential catalysis polar monomer polymerization, successively be synthesized, and their catalytic activity is verified (reference: H. L. Chen, S. Dutta, P. Y. Huang and C. C. Lin
organometallics,
31(5), 2016 – 2025,2012; D. V. Vitanova, F. Hampel and K. C. Hultzsch,
j. Organomet. Chem.,
690, 5182,2005).In addition, by the modification of the ligand structure to the metal center coordination, regulate and control solid and the electronic effect of part, and then regulate the activity of catalyzer and the selectivity large study hotspot in this field especially.In recent years, development along with Organolanthanide Chemistry, many novel rare earth metal organic compound are successfully synthesized, and increasing rare earth metal complex is found that polar monomer is had to good catalytic activity (G. Li, M. Lamberti, M. Mazzeo, D. Pappalardo
organometallics,
31, 1180 – 1188,2012).
Up to the present, although utilize containing large steric hindrance part as the rare earth metal complex of the parts such as amidino groups particularly the double-core rare earth metal complex to polar monomer as caprolactone, the catalyzed polymerization of rac-Lactide appears in the newspapers, but the report of the catalyzing of rare-earth metal system of the efficient controlled catalysis caprolactone isopolarity monomer polymerization of energy is rarer (J. P. Yang still, P. Xu, Y. J. Luo
chin. J. Chem.,
28, 457. 2010).
Summary of the invention
The purpose of this invention is to provide can efficient, controlled catalysis rac-Lactide, the new double-core rare-earth metal catalyst of caprolactone polar monomer polymerization and preparation method thereof and application.
New double-core catalyzing of rare-earth metal system provided by the invention, be in the rare earth compounding molecule two rare earth respectively with substituting group amidino groups (NCN) the chelating coordination of the large steric hindrance of two phenyl bridgings, respectively connect two alkyl, its structure is as follows simultaneously:
Wherein, Ln is rare earth metal, and Ln can be: scandium (Sc), yttrium (Y) or all lanthanon, and as lanthanum (La), neodymium (Nd), samarium (Sm), lutetium (Lu) etc.
Claim that catalyzer of the present invention is phenyl bridging amidino groups double-core rare-earth metal catalyst.
The present invention has studied the synthetic of such title complex, and to the type compound to some polar monomers, be mainly that the catalyzed polymerization performance to rac-Lactide, caprolactone is studied.We have investigated the impact on such catalyst system reactive behavior of temperature of reaction, time and rare earth ion radius size.Find that such title complex all has good catalyzed polymerization effect to caprolactone and rac-Lactide.For example:
This catalyst rac-Lactide polymerization, its with monomer be under the condition of 100:1 in mass ratio, in toluene solution or in THF solution, show very high catalytic activity.Its with monomer be under the condition of 100:1 in mass ratio, under lower temperature condition as 30 ℃ under also show higher catalytic activity.
This catalyst caprolactone polymerization, its with monomer by the condition of 1000:1 in mass ratio under in toluene solution or in THF solution, show very high catalytic activity.It is being pressed under the condition of 1000:1 under differing temps as 0 ℃ with monomer, and 25 ℃ also show very high catalytic activity.
This catalyzer is showing very high catalytic activity from monomer for example, by different ratio (300:1,500:1,700:1 etc.) condition under in toluene solution.
The synthetic method of phenyl bridging amidino groups double-core rare-earth metal catalyst in the present invention is described below, and concrete steps are as follows:
One, part is synthetic: under the anhydrous and oxygen-free condition, first by paradibromobenzene with
n the BuLi reaction makes the two lithium salts of phenyl, then, by the two lithium salts of phenyl and 2,6-diisopropyl phenyl Carbodiimide reaction, finally hydrolysis, make the two amidine ligands of corresponding phenyl.
Two, the preparation of rare earth metal complex: two kinds of methods are arranged.Method 1 is the matter solution, is about to amidino groups part and the rare earth trialkyl compound L nR of phenyl bridging
3reaction, obtain corresponding double-core rare earth dialkyl group title complex, productive rate 40～60%.Method 2 is one kettle ways, being about to two amidino groups parts reacts with butyllithium, reaction mixture is splashed in the rare earth trichloride of THF solvation, then direct and adjacent methyl N, the lithium salts reaction of accelerine, can obtain corresponding title complex, with toluene and normal hexane mixed solvent recrystallization, productive rate 50%～65%.
One, part is synthetic, and its reaction formula is:
Wherein, (i) excessive butyllithium, hexane solution is the RN=C=NR of twice equivalent (R=2,6-(ii)
i pr
2-C
6h
3-), in tetrahydrofuran solution, 12 hours.(iii) excessive water, 1 hour.
Two, the preparation of rare earth metal complex:
Method 1, reaction formula is:
Method 2, reaction formula is:
Wherein, (i) butyllithium of twice equivalent, tetrahydrofuran solution is the YCl of twice equivalent (ii)
3in tetrahydrofuran solution, 12 hours.(iii) the Li of four times of equivalents (
o-CH
2c
6h
4nMe
2).
Phenyl bridging amidino groups double-core rare-earth metal catalyst provided by the invention can be used for catalysis caprolactone or rac-Lactide polymerization, polymerization temperature is 0 ℃～100 ℃ (preferred polymerization temperature is 25 ℃～70 ℃), the transformation efficiency of monomer can reach 100%, can obtain that molecular weight is controlled, the macromolecular material of narrow molecular weight distribution, and for caprolactone, number-average molecular weight and transformation efficiency are linear, and molecular weight distribution is less than 1.5.By controlling metal center and monomer mole ratio, can also control the number-average molecular weight of product, thereby obtain the different macromolecular material of physico-chemical property.Metallic appearance, double-core effect, temperature effective all have obvious impact to reaction.Change reaction conditions and can also further improve position and the stereoselectivity of polyreaction.Novel phenyl bridging amidino groups double-core catalyzing of rare-earth metal system shown in the present is to caprolactone, and rac-Lactide has good catalyzed polymerization performance.Particularly can under gentle condition, realize the efficient controllable polymerization of caprolactone.
The concrete steps of catalyzed polymerization are as follows:
(1) dry monomer and solvent:
Lactide monomer (can buy and obtain from Acros), by vacuum-sublimation purifying (being less than 5 mmhg, 280 ℃), is saved backup under the anhydrous and oxygen-free condition.Caprolactone is at CaH
2under existence condition, reflux is 20 hours, then underpressure distillation obtains.Under the anhydrous and oxygen-free condition, save backup.Solvent toluene is under sodium silk and the existence of dimethyl benzophenone, is back to color and becomes purple or mazarine, then collects and leaves in the solvent bottle that the sodium sheet is housed, and is placed in glove box standby.
(2) catalytic polymerization of rac-Lactide:
Under the anhydrous and oxygen-free condition, get the above-mentioned catalyzer of a certain amount of (more than being generally 0.01mmol), put into sample bottle, the toluene that adds 10 ~ 20mL left and right dissolves, and its solution is added to dropping funnel, and take a certain amount of rac-Lactide in eggplant-shape bottle, rac-Lactide: catalyzer=100 ~ 5000(mol ratio), by dropping funnel and eggplant-shape bottle assembling, the maintenance system is airtight, shifts out glove box, be placed in the water-bath of 25-70 ℃, open the cock of dropping funnel, catalyzer is splashed in solution, stir.Reaction times was controlled in 1 hour.
Termination reaction: rapidly to the ethanolic soln quencher that the contains 5-10% hydrochloric acid reaction of injecting 2-5mL in system.Stir more than 10 minutes, add gradually a large amount of normal hexanes, the gained solid is put into the vacuum drying oven drying, under 60-80 ℃ of conditions, is dried to constant weight.The gel permeation chromatography for molecular weight of polymkeric substance (GPC, Waters 410 1515_2707_2414 systems) is measured.
(3) solution polymerization process of caprolactone:
Under the anhydrous and oxygen-free condition, get the catalyzer of a certain amount of (more than being generally 0.01 mmol), put into sample bottle, the toluene that adds 10 ~ 20 ml dissolves, and its solution is added to dropping funnel, and measure a certain amount of caprolactone in eggplant-shape bottle, caprolactone: catalyzer=100 ~ 10000(mol ratio), by dropping funnel and eggplant-shape bottle assembling, the maintenance system is airtight, shifts out glove box, be placed in the water-bath of 25-70 ℃, open the cock of dropping funnel, catalyzer is splashed in solution, stir.Reaction times was controlled in 10 minutes.
Termination reaction: inject the ethanolic soln quencher reaction that 2-5 mL contain 5-10% hydrochloric acid rapidly in system.Stir more than 10 minutes, add gradually a large amount of normal hexanes, the gained solid is put into the vacuum drying oven drying, under 60-80 ℃ of conditions, is dried to constant weight.The gel permeation chromatography for molecular weight of polymkeric substance (GPC, Waters 410 1515_2707_2414 systems) is measured.
Beneficial effect:
The catalyst system of phenyl bridging amidino groups double-core rare earth metal complex of the present invention all embodies high catalytic activity and the obvious feature of living polymerization in the reaction of catalysis rac-Lactide and caprolactone polymerization.Under 70 ℃ of conditions, while using the metal complexes of yttrium, the reaction times is 1 hour, and lactide conversions reaches 90%.Use the poly-transformation efficiency that can realize 100% that is incorporated in 10 minutes that the metal complexes of yttrium can also the catalysis caprolactone.The difference of metal, also cause the difference of catalyzed reaction effect.
Embodiment
Synthesizing of embodiment 1 phenyl bridge ligand, its preparation process is as shown below:
Wherein, (i) excessive butyllithium, hexane solution is the RN=C=NR of twice equivalent (R=2,6-(ii)
i pr
2-C
6h
3-), in tetrahydrofuran solution, 12 hours.(iii) excessive water, 1 hour.
Take paradibromobenzene 0.476 g (2 mmol) and be dissolved in the hexane solution of 40 mL, at room temperature in this solution, slowly add 2.4 mL
n buLi(6 mmol) this solution is obtained to the lithium salts of Off-white solid in 12 hours 80 ℃ of heating, this emulsion filters by sand core funnel and washs three times (3 * 10 mL) afterwards with hexane solution, the white solid obtained is dissolved in 20 mL tetrahydrofuran solutions, then add 1.45 g(4 mmol in this solution) tetrahydrofuran solution of carbodiimide, solution is rice white.Stirring reaction after 12 hours with after excessive water quencher, obtaining saffron clarified liq.The organism obtained by extracted with diethyl ether obtains target product phenyl bridging amidino groups part (1) 0.48 g at-40 ℃ of lower crystallization purifyings in hexane solution, and productive rate is 30%.
1H?NMR?(400?MHz,?CDCl
3,?25℃):?δ?=?0.85?[d,?
J＝6.0?Hz,?12H,?CH(C
H 3 )
2],?0.94?[d,?
J＝6.8?Hz,?12H,?CH(C
H 3 )
2],?1.16?[d,?
J＝6.0?Hz,?12H,?CH(C
H 3)
2],?1.32?[d,?
J＝6.0?Hz,?12H,?CH(C
H 3)
2],?3.10?3.15?[m,?8H,?C
H(CH
3)
2],?5.65?(s,?2H,?N
H),?6.95?7.23?ppm?(m,?16H,?Ar
H)。
13C?NMR?(100?MHz,?CDCl
3,?25℃):?
δ=?22.4,?22.5,?24.3,?25.5?[CH(
CH
3)
2],?28.5?[
CH(CH?
3)
2],?28.8?[
CH(CH
3)
2],?123.5,?123.2,?127.7,?127.8,?133.9,?136.0,?139.2,?143.5,?145.3?(ArC),?153.5?ppm?(NCN)。The results of elemental analyses demonstration, the carbon content of this part is 83.70, and hydrogen richness is 9.57, and nitrogen content is 7.12, with theoretical value, conforms to.
Synthesizing of embodiment 2 title complexs 2,3,4.
Method 1. reaction formula are:
Taking 0.402 g (0.5 mmol) part is dissolved in 20 mL tetrahydrofuran (THF)s or toluene solution, 1 mmol Y rare earth is all joined to compound to be dissolved in 10 mL tetrahydrofuran (THF)s or toluene solution, part is added dropwise to and all joins in compound, 70 ℃ are reacted 24 hours, and after reaction finishes, solution becomes safran.Pump solution, drain rear recrystallization and obtain faint yellow solid product 0.83 g, productive rate is 55%.The nucleus magnetic resonance of title complex 2:
1h NMR (400 MHz, C
6d
6, 60 ℃):
δ=0.8 (s, 24 H, CH
me 2), 1.28 (d, 24 H,
3 j h-H=4.0 Hz, CH
me 2), 1.74 (s, 8 H, C
h 2c
6h
4nMe
2), 2.31 (s, 24 H, CH
2c
6h
4n
me 2), 3.52 (m, 8 H,
cHme
2), 6.57-6.42 (br, 8H, Ar), 7.00-6.80 ppm (br, 24H, Ar).
13c NMR (100 MHz, C
6d
6, 25 ℃):
δ=24.99 (br, CH
me 2), 25.36 (s, CH
me 2), 28.44 (s,
chMe
2), 46.16 (br,
o-CH
2c
6h
4n
me 2), 47.42 (d,
j y-C=30 Hz,
ch
2c
6h
4nMe
2), 118.51 (s, Ar), 120.46, (s, Ar), 124.36 (s, Ar), 124.81 (s, Ar), (126.86 br, Ar), 128.65 (s, Ar), 128.85 (s, Ar), 133.36 (d, Ar), 142.22 (s, Ar), (143.21 s, Ar), 143.40 (s, Ar), (145.48 s, Ar), 174.29 ppm (s, N
cn).The results of elemental analyses demonstration, the carbon content of this title complex is 72.90, and hydrogen richness is 7.98, and nitrogen content is 7.39, with theoretical value, conforms to.The nucleus magnetic resonance of title complex 3:
1h NMR (400 MHz, C
6d
6, 60 ℃):
δ=0.8 (s, 24 H, CH
me 2), 1.28 (d, 24 H,
3 j h-H=4.0 Hz, CH
me 2), 1.74 (s, 8 H, C
h 2c
6h
4nMe
2), 2.31 (s, 24 H, CH
2c
6h
4n
me 2), 3.52 (m, 8 H,
cHme
2), 6.57-6.42 (br, 8H, Ar), 7.00-6.80 ppm (br, 24H, Ar).
13c NMR (100 MHz, C
6d
6, 25 ℃):
δ=24.99 (br, CH
me 2), 25.36 (s, CH
me 2), 28.44 (s,
chMe
2), 46.16 (br,
o-CH
2c
6h
4n
me 2), 47.42 (d,
j y-C=30 Hz,
ch
2c
6h
4nMe
2), 118.51 (s, Ar), 120.46, (s, Ar), 124.36 (s, Ar), 124.81 (s, Ar), (126.86 br, Ar), 128.65 (s, Ar), 128.85 (s, Ar), 133.36 (d, Ar), 142.22 (s, Ar), (143.21 s, Ar), 143.40 (s, Ar), (145.48 s, Ar), 174.29 ppm (s, N
cn).The results of elemental analyses demonstration, the carbon content of this title complex is 66.83, and hydrogen richness is 8.17, and nitrogen content is 6.63.With theoretical value, conform to.The nucleus magnetic resonance of title complex 4:
1h NMR (400 MHz, C
6d
6, 60 ℃):
δ=0.83 (s, 24 H, CH
me 2), 1.34 (d, 24 H,
3 j h-H=4.0 Hz, CH
me 2), 1.86 (s, 8 H, C
h 2c
6h
4nMe
2), 2.35 (s, 24 H, CH
2c
6h
4n
me 2), 3.68 (m, 8 H,
cHme
2), 6.62-6.45 (br, 8H, Ar), 7.05-6.79 ppm (br, 24H, Ar).
13c NMR (100 MHz, C
6d
6, 25 ℃):
δ=25.07 (br, CH
me 2), 26.32 (s, CH
me 2), 27.96 (s,
chMe
2), 47.03 (s,
o-CH
2c
6h
4n
me 2), 47.95 (br,
ch
2c
6h
4nMe
2), 117.31 (s, Ar), 121.14 (s, Ar), (124.57 br, Ar), 125.35 (s, Ar), 126.18 (s, Ar), 129.12 (s, Ar), 129.39 (s, Ar), (133.05 s, Ar), 142.89 (s, Ar), (143.28 s, Ar), 148.25 (s, Ar), (149.00 s, Ar), 174.21 ppm (s, N
cn). the results of elemental analyses demonstration, the carbon content of this title complex is 72.77, and hydrogen richness is 8.43, and nitrogen content is 7.29.With theoretical value, conform to.
Method 2. reaction formula are:
Wherein, (i) butyllithium of twice equivalent, tetrahydrofuran solution is the LnCl of twice equivalent (ii)
3in tetrahydrofuran solution, 12 hours.(iii) the Li of four times of equivalents (
o-CH
2c
6h
4nMe
2).
Take the two amidine ligands of 0.321 g (0.4 mmol) phenyl bridging and be dissolved in 30 mL tetrahydrofuran (THF)s, at room temperature slowly drip butyllithium (0.8 mmol) solution, continue reaction 2h and make to react completely.Reaction solution is splashed into to YCl
3in the tetrahydrofuran solution of (0.8 mmol with 10 mL THF solvation 5 hours) in advance, under room temperature, reaction is 8 hours.At room temperature in reaction solution, drip
o-LiCH
2c
6h
4nMe
2solution 0.2258 g (1.6 mmol) is dissolved in 5 mL THF, and reaction is spent the night.Drain solvent, obtain pale yellow powder, use the toluene extraction product, remove by filter byproduct of reaction LiCl, the mother liquor condensing crystal is obtained to faint yellow solid product 0.98 g(productive rate 65%).
Table one. the representative data of poly-propiolactone
| run | Cat. | t(℃) | conv b (%) | M n,calc c | M n,exp d | M w/ M n |
| 1 | 2 | 30 | 83.2 | 2998 | 9770 | 1.97 |
| 2 | 2 | 70 | 90.1 | 3247 | 11166 | 1.76 |
| 3 e | 2 | 70 | 79.5 | 2865 | 6777 | 1.41 |
| 4 | 3 | 70 | 91.2 | 3287 | 11823 | 1.88 |
| 5 | 4 | 70 | 80.4 | 2897 | 7891 | 1.27 |
| 6 f | YR | 70 | 95.2 | 3431 | 5064 | 2.05 |
apolymerizing condition: [D, L-LA]
0/ [title complex]
0=100, title complex mole number=0.014 mmol, 10ml toluene, t=1h;
bproductive rate passes through
1h NMR spectrogram (CDCl
3).
ccalculate productive rate by ([D, L-LA]/4[title complex]
0) * 144.14 * X (X=conv), organize 6, calculates productive rate by ([D, L-LA]
0/ 2[YR]
0) * 144.14 * X (X=conv).
dtest is by GPC (vs polystyrene standards).
ein THF.
fyR=(NCN
dipp) Y (CH
2c
6h
4nMe
2-o)
2, [D, L-LA]
0/ [YR]
0=50.
Table two. the representative data of polycaprolactone
| run | Cat. | [CL] 0:[Cat.] 0 | T (℃) | Time (min) | Conv b(%) | Yield c( %) | M n,calc d | M n,(exp) e | M w/ M n |
| 1 | 2 | 1000:1 | 0 | 10 | 95 | 92 | 27108 | 80875 | 1.4 |
| 2 | 2 | 1000:1 | 25 | 10 | 100 | 92 | 28535 | 87694 | 1.32 |
| 3 | 2 | 1000:1 | 25 | 1 | 96 | 90 | 27393 | 92116 | 1.35 |
| 4 | 2 | 1000:1 | 25 | 0.5 | 81 | 75 | 23113 | 76312 | 1.32 |
| 5 f | 2 | 1000:1 | 25 | 10 | 90 | 85 | 25682 | 59945 | 1.33 |
| 6 | 3 | 1000:1 | 25 | 10 | 94 | 90 | 26823 | 83621 | 1.32 |
| 7 | 4 | 1000:1 | 25 | 10 | 85 | 83 | 24255 | 68634 | 1.31 |
| 8 g | YR | 500:1 | 25 | 10 | 100 | 93 | 28535 | 72677 | 1.33 |
| 9 | 2 | 100:1 | 25 | 10 | 100 | 91 | 2854 | 11471 | 1.33 |
| 10 | 2 | 300:1 | 25 | 10 | 100 | 93 | 8561 | 34701 | 1.24 |
| 11 | 2 | 500:1 | 25 | 10 | 100 | 91 | 14268 | 53320 | 1.28 |
| 12 | 2 | 700:1 | 25 | 10 | 100 | 94 | 19975 | 70079 | 1.23 |
| 13 | 2 | 1000:1 | 25 | 10 | 100 | 92 | 28535 | 90136 | 1.18 |
apolymerizing condition: title complex mole number=0.0094 mmol, 20 mL toluene, group 9-13, title complex mole number=0.0094 mmol, 40 mL toluene;
bproductive rate passes through
1h NMR spectrogram (CDCl
3).
cisolated yield
dtest is by by ([CL]
0/ 4[title complex]
0) * 114.14 * X (X=conv), organize 8, and test is by ([CL]
0/ 2[YR]
0) * 114.14 * X (X=conv).
etest is by GPC (vs polystyrene standards).
fin THF.
gyR=(NCN
dipp) Y (CH
2c
6h
4nMe
2-o)
2, [CL]
0/ [YR]
0=500.
Embodiment 3
Take 0.021 g (0.014 mmol) title complex 2 in sample bottle, dissolve with 2 mL toluene, then take 200 mg (1.4 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 30 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of dry polylactide solid 166.4 mg that obtain of vacuum drying oven, transformation efficiency is about 83.2%.Use gpc analysis, record the molecular weight 9770 of polymkeric substance, PDI is 1.97.
Embodiment 4
Take 0.021 g (0.014 mmol) title complex 2 in sample bottle, dissolve with 2 mL toluene, then take 200 mg (1.4 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 70 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of dry polylactide solid 180.2 mg that obtain of vacuum drying oven, transformation efficiency is about 90.1%.Use gpc analysis, record the molecular weight 11166 of polymkeric substance, PDI is 1.76.
Embodiment 5
Take 0.021 g (0.014 mmol) title complex 2 in sample bottle, dissolve with 2 mL THF, then take 200 mg (1.4 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 70 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of vacuum drying ovens are dried to constant weight, obtain polylactide solid 159.0 mg, and transformation efficiency is about 79.5%.Use gpc analysis, record the molecular weight 6777 of polymkeric substance, PDI is 1.41.
Embodiment 6
Take 0.023 g (0.014 mmol) title complex 3 in sample bottle, dissolve with 2 mL toluene, then take 200 mg (1.4 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 70 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of dry polylactide solid 182.4 mg that obtain of vacuum drying oven, transformation efficiency is about 91.2%.Use gpc analysis, record the molecular weight 11823 of polymkeric substance, PDI is 1.88.
Embodiment 7
Take 0.020 g (0.014 mmol) title complex 4 in sample bottle, dissolve with 2 mL toluene, then take 200 mg (1.4 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 70 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of dry polylactide solid 160.8 mg that obtain of vacuum drying oven, transformation efficiency is about 80.4%.Use gpc analysis, record the molecular weight 7891 of polymkeric substance, PDI is 1.27.
Embodiment 8
Take 0.011 g (0.014 mmol) title complex YR (NCN
dipp) Y (CH
2c
6h
4nMe
2-
o)
2, in sample bottle, with 2 mL toluene, dissolve, then take 100 mg (0.7 mmol) rac-Lactide and have in the eggplant-shape bottle of 8 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, under 70 ℃ of conditions, dropping funnel is opened catalyzer is added rapidly.React after 1 hour, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Slowly add hexane solution under stirring.Until solid precipitates fully, the liquid that inclines, the white solid of the polylactide obtained.60 ℃ of dry polylactide solid 95.2 mg that obtain of vacuum drying oven, transformation efficiency is about 95.2%.Use gpc analysis, record the molecular weight 5064 of polymkeric substance, PDI is 2.05.
Embodiment 9
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 0 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.60 ℃ of vacuum drying ovens are dried to constant weight and obtain polycaprolactone solid 920 mg, and transformation efficiency is about 92%.Record the molecular weight 80875 of polymkeric substance with gpc analysis, PDI is 1.4.
Embodiment 10
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.60 ℃ of vacuum drying ovens are dried to constant weight and obtain polycaprolactone solid 920 mg, and transformation efficiency is about 92%.Record the molecular weight 87694 of polymkeric substance with gpc analysis, PDI is 1.32.
Embodiment 11
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reaction 1min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.60 ℃ of vacuum drying ovens are dried to constant weight and obtain polycaprolactone solid 900 mg, and transformation efficiency is about 90%.Record the molecular weight 92116 of polymkeric substance with gpc analysis, PDI is 1.35.
Embodiment 12
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 30 s, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 750 mg, and transformation efficiency is about 75%.The molecular weight that records polymkeric substance with gpc analysis is that 76312, PDI is 1.32.
Embodiment 13
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL THF, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL THF in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 850 mg, and transformation efficiency is about 85%.Record the molecular weight 59945 of polymkeric substance with gpc analysis, PDI is 1.33.
Embodiment 14
Take 0.016 g (0.0094 mmol) title complex 3 in sample bottle, dissolve with 4 mL THF, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL THF in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 900 mg, and transformation efficiency is about 90%.Record the molecular weight 83621 of polymkeric substance with gpc analysis, PDI is 1.32.
Embodiment 15
Take 0.013 g (0.0094 mmol) title complex 4 in sample bottle, dissolve with 4 mL THF, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL THF in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 830 mg, and transformation efficiency is about 83%.Record the molecular weight 68634 of polymkeric substance with gpc analysis, PDI is 1.31.
Embodiment 16
Take 0.015 g (0.0188 mmol) title complex YR (NCN
dipp) Y (CH
2c
6h
4nMe
2-
o)
2, in sample bottle, with 4 mL THF, dissolve, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 15 mL THF in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 465 mg, and transformation efficiency is about 93%.Record the molecular weight 72677 of polymkeric substance with gpc analysis, PDI is 1.33.
Embodiment 17
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 0.1 mL (0.94 mmol) caprolactone and have in the eggplant-shape bottle of 36 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 910 mg, and transformation efficiency is about 91%.Record the molecular weight 11471 of polymkeric substance with gpc analysis, PDI is 1.33.
Embodiment 18
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 0.3 mL (2.82 mmol) caprolactone and have in the eggplant-shape bottle of 36 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 930 mg, and transformation efficiency is about 93%.Record the molecular weight 34701 of polymkeric substance with gpc analysis, PDI is 1.24.
Embodiment 19
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 0.5 mL (4.7 mmol) caprolactone and have in the eggplant-shape bottle of 36 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 910 mg, and transformation efficiency is about 91%.Record the molecular weight 53320 of polymkeric substance with gpc analysis, PDI is 1.28.
Embodiment 20
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 0.7 mL (6.58 mmol) caprolactone and have in the eggplant-shape bottle of 36 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 940 mg, and transformation efficiency is about 94%.Record the molecular weight 70079 of polymkeric substance with gpc analysis, PDI is 1.23.
Embodiment 21
Take 0.014 g (0.0094 mmol) title complex 2 in sample bottle, dissolve with 4 mL toluene, then measure 1 mL (9.4 mmol) caprolactone and have in the eggplant-shape bottle of 36 mL toluene in adding.Dropping funnel and eggplant-shape bottle are assembled, open and stir, at 25 ℃ of temperature, dropping funnel is opened catalyzer is added rapidly.After reacting 10 min, get a part of reaction solution and drain and do nuclear-magnetism and judge productive rate with this.And add the ethanolic soln cancellation reaction of 1 mL containing 5% concentrated hydrochloric acid in system.Stir lower slow hexane solution.Until solid precipitates fully, the liquid that inclines, the white solid of the polycaprolactone obtained.Head product is placed in vacuum drying oven, under 60 ℃ of conditions, is dried to constant weight, obtains polycaprolactone solid 920 mg, and transformation efficiency is about 92%.Record the molecular weight 90136 of polymkeric substance with gpc analysis, PDI is 1.18.
Claims (5)
1. a phenyl bridging amidino groups double-core rare-earth metal catalyst, it is characterized in that: in the rare earth compounding molecule two rare earth metals with respectively with two large steric hindrance substituting group amidino groups chelatings of phenyl bridging, each connects respectively two alkyl simultaneously, and its structure is shown below:
Wherein, Ln is rare earth metal scandium, yttrium or lanthanon.
2. the synthetic method of a phenyl bridging amidino groups double-core rare-earth metal catalyst as claimed in claim 1, its concrete steps are as follows:
Step 1, part synthetic: under the anhydrous and oxygen-free condition, first by paradibromobenzene with
n the BuLi reaction makes the two lithium salts of phenyl, then, by the two lithium salts of phenyl and 2,6-diisopropyl phenyl Carbodiimide reaction, finally is hydrolyzed, and makes the amidino groups part of corresponding phenyl bridging;
The preparation of step 2, rare earth metal complex has two kinds of methods:
Method 1 is the matter solution, is about to amidino groups part and the rare earth trialkyl compound L n (CH of phenyl bridging
2c
6h
4-
o-NMe
2)
3reaction, obtain corresponding double-core rare earth dialkyl group title complex;
Method 2 is one kettle ways, the amidino groups part that is about to the phenyl bridging reacts with butyllithium, reaction mixture is splashed in the rare earth trichloride of THF solvation, then direct and adjacent methyl N, the lithium salts reaction of accelerine, obtain corresponding rare earth metal complex, with toluene and normal hexane mixed solvent recrystallization.
3. the application of phenyl bridging amidino groups double-core rare-earth metal catalyst as claimed in claim 1 in catalysis caprolactone or rac-Lactide polymerization.
4. application according to claim 3 is characterized in that the step of rac-Lactide catalyzed polymerization is:
Under the anhydrous and oxygen-free condition, get the above described catalyzer of 0.01 mmol, put into sample bottle, the toluene that adds 10 ~ 200 mL dissolves, and its solution is added to dropping funnel, and take rac-Lactide in eggplant-shape bottle, the mol ratio of rac-Lactide and catalyzer is 100 ~ 5000, by dropping funnel and eggplant-shape bottle assembling, the maintenance system is airtight, shifts out glove box, be placed in the water-bath of 25 ℃-70 ℃, open the cock of dropping funnel, catalyzer is splashed in solution, stir; Reaction times was controlled in 1 hour; Termination reaction: to the ethanolic soln quencher that the contains 5-10% hydrochloric acid reaction of injecting 2-5mL in system; Stir more than 10 minutes, add gradually a large amount of normal hexanes, the gained solid is put into the vacuum drying oven drying, is dried to constant weight under 60 ℃-80 ℃.
5. application according to claim 3 is characterized in that the step of caprolactone catalyzed polymerization is:
Under the anhydrous and oxygen-free condition, get the above-described catalyzer of 0.01 mmol, put into sample bottle, the toluene that adds 10 ~ 20 ml dissolves, and its solution is added to dropping funnel, separately gets caprolactone and is placed in eggplant-shape bottle, the mol ratio of caprolactone and catalyzer is 100 ~ 10000, by dropping funnel and eggplant-shape bottle assembling, the maintenance system is airtight, shifts out glove box, be placed in the water-bath of 25-70 ℃, open the cock of dropping funnel, catalyzer is splashed in solution, stir; Reaction times was controlled in 10 minutes;
Termination reaction: in system, inject the ethanolic soln quencher reaction that 2-5 mL contain 5-10% hydrochloric acid; Stir more than 10 minutes, add gradually a large amount of normal hexanes, the gained solid is put into the vacuum drying oven drying, under 60-80 ℃ of conditions, is dried to constant weight.
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