CN102250137B - 3,5-ditertbutyl salicylidene ethylenediamine iron complex, and preparation method and application thereof - Google Patents
3,5-ditertbutyl salicylidene ethylenediamine iron complex, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a 3,5-ditertbutyl salicylidene ethylenediamine iron complex, and an eparation method and application thereof. The structural formula of the complex is shown in the specifications. The preparation method comprises the following steps of: dissolving 3,5-ditertbutyl salicylaldehyde and ethanediamine in ethanol in a molar ratio of 2:(1-1.2), and reacting at the temperature ofbetween 70 and 80 DEG C for not less than 0.5 hour; dissolving a product and tetraethyl titanate in methylbenzene in a molar ratio of 1:(1-1.2), and reacting at the temperature of between 18 and 60 DEG C for not less than 2 hours; and adding an equimolar aqueous medium, reacting for not less than 3 hours with stirring, and crystallizing to obtain the 3,5-ditertbutyl salicylidene ethylenediamine iron complex. The dispersion degree of the molecular weight of polylactic acid prepared from the complex ranges from 1.09 to 1.24, and the complex has higher molecular weight controllability for ring opening of lactide; and the polylactic acid prepared from the complex can basically meet the requirements on molecular weight and dispersion degree in the field of bioengineering.
Description
Technical field
The present invention relates to the synthetic field of two schiff bases peptide title complexs, particularly 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex and its preparation method and application.
Background technology
Polylactic acid-based material is owing to having excellent biological compatibility and the biodegradability fields such as internal fixing, tissue engineering bracket, medical implantation, surgical sutures, medicine controlled releasing system that are widely used in fracturing.Because fracture internal fixing and tissue engineering bracket are higher to the requirement of strength of material, therefore have only the poly(lactic acid) of high molecular, low dispersity that actual application value is just arranged.High molecular weight polylactic acid is mainly obtained by rac-Lactide ring-opening polymerization under organometallic catalysis.Be main with organic tin catalyzer, particularly stannous octoate mainly at present.But because stannous octoate instability, easily decomposition when high temperature polymerization, the by product that produces makes in the polymerization process of poly(lactic acid) the generation of inevitable side reaction, make the dispersity of poly(lactic acid) increase, influence the mechanical property of poly-lactic acid in high molecular weight, and poly(lactic acid) is under the effect of the catalysis of stannous octoate and aided initiating, and the poly(lactic acid) weight-average molecular weight is not high yet.Therefore seek the focus that high catalytic activity catalyst becomes this area research.
Because the titanium material has erosion resistance and excellent biological compatibility, be applied clinically as bio-medical material widely, there are some researches show that also open loop has catalytic activity to titanium class organo-metallic to rac-Lactide simultaneously.In these researchs, though the titanium class organo-metallic that obtains all has the function of energy catalysis rac-Lactide mass polymerization, but synthetic polylactic acid molecule amount and molecular weight, dispersity still can not satisfy the demand, particularly bone reparation and tissue engineering bracket material of biomedical engineering field.
Summary of the invention
One of purpose of the present invention is to provide a kind of pair of schiff bases peptide title complex, and it can be used for D as catalysis, and the L-rac-Lactide synthesizes the schiff bases titanium complex.
For achieving the above object, technical scheme of the present invention is:
3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex, its structural formula is shown in I:
Ⅰ
T-Bu is the tertiary butyl in the structural formula.
Two of purpose of the present invention is to provide the preparation method of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex, and this method is simple to operate, and the yield height is applicable to scale operation.
For achieving the above object, technical scheme of the present invention is:
The preparation method of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex specifically may further comprise the steps:
The preparation of A part
With structural formula shown in II 3,5-di-tert-butyl salicylaldehyde and quadrol are dissolved in the ethanol with the mol ratio of 2:1-1.2, under 70 ~ 80 ℃ of conditions the reaction be not less than 0.5 hour, get structural formula shown in III 3,5-di-tert-butyl salicylaldehyde contracting quadrol part;
The preparation of B title complex
With steps A gained 3,5-di-tert-butyl salicylaldehyde contracting quadrol part and tetraethyl titanate are dissolved in the toluene with the mol ratio of 1:1 ~ 1.2, temperature is reacted down for 18 ~ 60 ℃ and is not less than 2 hours, add and 3 again, 5-di-tert-butyl salicylaldehyde contracting quadrol part is equimolar, stirring reaction was not less than 3 hours, and crystallization gets 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex under the reaction solution room temperature.
Further, in the steps A, with 3,5-di-tert-butyl salicylaldehyde, quadrol and dehydrated alcohol dissolve to abundant according to the mixed in molar ratio of 2:1-1.2, react 0.5 ~ 1 hour suction filtration under 70 ~ 80 ℃ of conditions, alcohol is washed 2 ~ 3 times, dry 3, the 5-di-tert-butyl salicylaldehyde contracting quadrol part that gets.
Further; with steps A gained 3; 5-di-tert-butyl salicylaldehyde contracting quadrol part, tetraethyl titanate and toluene dissolve to abundant with the mixed in molar ratio of 1:1-1.2; under the nitrogen protection; temperature was reacted 2 hours down for 18 ~ 60 ℃; add and 3 again; 5-di-tert-butyl salicylaldehyde contracting quadrol part is equimolar, stirring reaction 3 hours, and crystallization gets yellow bulk crystals under the reaction solution room temperature; filter; toluene dissolving-recrystallization twice filters, and vacuum-drying is to constant weight; get 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.
Further, described toluene is the toluene after also distilling with the hydrolith processed.
Three of purpose of the present invention is to provide the application of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex, and this uses the high molecular of the poly(lactic acid) of preparation, and dispersity is low.
For achieving the above object, technical scheme of the present invention is:
3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is at preparation D, and the ring-opening polymerization of L-rac-Lactide becomes Application of Catalyst in the poly(lactic acid).
Four of purpose of the present invention is to provide the preparation method of poly(lactic acid), and this method is simple to operate, is applicable to scale operation.
For achieving the above object, technical scheme of the present invention is:
The preparation method of poly(lactic acid), with D, the mol ratio of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is at 2300-3000:1, under 150-180 ℃, reacts 6-20 hour, gets poly(lactic acid).
Further, with D, the mol ratio of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is at 2600:1, under 160 ℃, reacts 16 hours, gets poly(lactic acid).
Beneficial effect of the present invention is: all in 1.09 ~ 1.24 scopes, this shows this catalyzer, and open loop has higher molecular weight controllability to the molecular weight dispersity of employing 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex gained poly(lactic acid) to rac-Lactide; The poly(lactic acid) of this complex-catalyzed preparation is expected to use in this field in the demand that can satisfy biomedical engineering field aspect molecular weight and the dispersity substantially.More beneficial effect will embody in embodiment.
Description of drawings
Fig. 1 is the infrared spectra of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex;
Fig. 2 is 3,5-di-tert-butyl salicylaldehyde contracting quadrol part
1H-NMR;
Fig. 3 is 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex
1H-NMR;
Fig. 4 is 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex single crystal structure figure;
Fig. 5 is the TG figure of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex;
Fig. 6 is the DSC figure of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.
Embodiment
To help further to understand the present invention by following embodiment, but not limit content of the present invention.
Following embodiment shows not ipsilateral of the present invention, and given data comprise the operational condition of synthesizing of part and title complex and polyreaction etc.Unless stated otherwise, the synthetic and polyreaction of metal complexes is all carried out under nitrogen protection.Solvent all uses the method for standard to remove water treatment.
Magnetic stirring apparatus is being housed, in the reactor of reflux condensing tube and thermometer, add 3 of 9.4g (0.04mol), the 5-di-tert-butyl salicylaldehyde is in the dehydrated alcohol of 60ml, ℃ backflow dissolving of intensification degree to 60, quadrol is the ratio adding of 2:1 according to 3,5-di-tert-butyl salicylaldehyde and its mol ratio, temperature rising reflux 1 hour.Produce a large amount of yellow mercury oxides, suction filtration, hot absolute ethanol washing, vacuum-drying to constant weight gets 3,5-di-tert-butyl salicylaldehyde contracting quadrol part.Productive rate is 79.32%.
Magnetic stirring apparatus is being housed, in the reactor of reflux condensing tube and thermometer, add 3 of 9.4g (0.04mol), the 5-di-tert-butyl salicylaldehyde is in the dehydrated alcohol of 60ml, ℃ backflow dissolving of intensification degree to 60, quadrol is the ratio adding of 2:1.1 according to 3,5-di-tert-butyl salicylaldehyde and its mol ratio, temperature rising reflux 1 hour.Produce a large amount of yellow mercury oxides, filter, hot absolute ethanol washing, vacuum-drying to constant weight gets 3,5-di-tert-butyl salicylaldehyde contracting quadrol part.Productive rate is 78.99%.
Magnetic stirring apparatus is being housed, in the reactor of reflux condensing tube and thermometer, add 3 of 9.4g (0.04mol), the 5-di-tert-butyl salicylaldehyde is in the dehydrated alcohol of 60ml, ℃ backflow dissolving of intensification degree to 60, quadrol is the ratio adding of 2:1.2 according to 3,5-di-tert-butyl salicylaldehyde and its mol ratio, temperature rising reflux 1 hour.Produce a large amount of yellow mercury oxides, filter, hot absolute ethanol washing, vacuum-drying to constant weight gets 3,5-di-tert-butyl salicylaldehyde contracting quadrol part.Productive rate is 79.01%.
Magnetic stirring apparatus is being housed; in the reactor of nitrogen protection; add 2.9564g(0.006mol) 3; 5-di-tert-butyl salicylaldehyde contracting quadrol part is in the toluene that anhydrates of 40ml; dissolving is the mol ratio adding tetraethyl titanate of 1:1 with pipettor according to part and tetraethyl titanate, and stirring reaction is 2 hours under 25 ℃ room temperature; add and the equimolar distilled water of tetraethyl titanate again, stir 3h.Crystallization gets yellow bulk crystals under the reaction solution room temperature, filters, and the toluene dissolving-recrystallization twice that anhydrates filters, and vacuum-drying gets yellow solid 3 to constant weight, 5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.Yield is 65.11%.
Magnetic stirring apparatus is being housed; in the reactor of nitrogen protection; add 2.9564g(0.006mol) 3; 5-di-tert-butyl salicylaldehyde contracting quadrol part is in the toluene that anhydrates of 40ml; dissolving is the mol ratio adding tetraethyl titanate of 1:1.1 with pipettor according to part and tetraethyl titanate, and stirring reaction is 2 hours under 25 ℃ room temperature; add and the equimolar distilled water of tetraethyl titanate again, stir 3h.Crystallization gets yellow bulk crystals under the reaction solution room temperature, filters, and the toluene dissolving-recrystallization twice that anhydrates filters, and vacuum-drying gets yellow solid 3 to constant weight, 5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.Yield is 64.91%.
Magnetic stirring apparatus is being housed; in the reactor of nitrogen protection; add 2.9564g(0.006mol) 3; 5-di-tert-butyl salicylaldehyde contracting quadrol part is in the toluene that anhydrates of 40ml; dissolving is the mol ratio adding tetraethyl titanate of 1:1.2 with pipettor according to part and tetraethyl titanate, and stirring reaction is 2 hours under 25 ℃ room temperature; add and the equimolar distilled water of tetraethyl titanate again, stir 3h.Crystallization gets yellow bulk crystals under the reaction solution room temperature, filters, and the toluene dissolving-recrystallization twice that anhydrates filters, and vacuum-drying gets yellow solid 3 to constant weight, 5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.Yield is 63.87%.
The sign of third part part and title complex
This part has adopted infrared spectroscopy, nucleus magnetic resonance, single crystal structure analytical method, thermal analysis system etc. to 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex and intermediate product 3 thereof, the sign of 5-di-tert-butyl salicylaldehyde contracting quadrol part.
Embodiment 73, and the infrared spectra of 5-di-tert-butyl salicylaldehyde contracting quadrol part detects
The KBr pressed disc method, the infrared and microscopic system (U.S., Perkin Elmer company) of Spectrum GX type.Fig. 1 shows, 1436.07cm
-1~ 1553.51cm
-1The place is the breathing vibration peak of Ar-H; 1618.93cm
-1The place is imido grpup (stretching vibration absorption peak CH=N-); 1274.03cm
-1The place is the stretching vibration peak of phenolic hydroxyl group (Ar-O); 3426.75 cm
-1The broad peak that the place occurs belongs to the water peak in the sample; 533.31cm
-1And 550.07cm
-1The place is respectively the stretching vibration peak of O-Ti and Ti-N key.
One, 3,5-di-tert-butyl salicylaldehyde contracting quadrol part
1H-NMR
Solvent: deuterochloroform CDCL
3(Fluka Chemica, heavy hydrogen content is not less than 99.8%); Interior mark: tetramethylsilane (TMS); Instrument: AV-500 type nuclear magnetic resonance spectrometer (Switzerland, Bruker company), operating frequency 500MHz.As shown in Figure 2,
δ=1.338ppm and δ=1.493ppm belong in two tertiary butyls on the phenyl ring-C
H 3The proton absorption peak; δ=3.951ppm belongs to-CH=N-C
H 2-CH
2The proton absorption peak of-middle methylene radical; δ=7.116 ~ 7.120ppm and δ=7.419 ~ 7.424ppm belongs to two proton absorption peaks on the phenyl ring; δ=8.431ppm belongs to-C
H=N-CH
2-CH
2-middle imido grpup proton absorption peak; δ=13.678ppm belongs to the proton absorption peak of hydroxyl on the phenyl ring.
Two, embodiment 4-6 make 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex
1The H-NMR(proton nmr spectra)
Solvent: deuterochloroform CDCL
3(Fluka Chemica, heavy hydrogen content is not less than 99.8%); Interior mark: tetramethylsilane (TMS); Instrument: AV-500 type nuclear magnetic resonance spectrometer (Switzerland, Bruker company), operating frequency 500MHz.
As shown in Figure 3, δ=1.272ppm and δ=1.363ppm belong on the phenyl ring on two tertiary butyls-CH
3The proton absorption peak; δ=3.377 ~ 3.389ppm and δ=4.412 ~ 4.423ppm belongs to-CH=N-CH
2The proton absorption peak of-middle methylene radical; δ=6.992 ~ 6.996ppm and δ=7.393 ~ 7.397ppm belongs to the absorption peak of two protons on the phenyl ring; δ=8.082ppm belongs to-proton absorption peak among the CH=N-; And be the proton absorption peak on the toluene that does not eliminate in the sample at δ=2.347ppm and δ=7.134 ~ 7.7.173ppm, δ=7.231ppm ~ 7.261ppm place in the collection of illustrative plates.
Contrast shown in Figure 23,5-di-tert-butyl salicylaldehyde contracting quadrol part and shown in Figure 33,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex
1The H-NMR collection of illustrative plates as can be known in the part spectrogram on the phenyl ring at δ=13.678ppm place the proton peak of phenolic hydroxyl group obviously disappear, Sauerstoffatom and Ti atomic bonding on the phenolic hydroxyl group on 3, the 5-di-tert-butyl salicylaldehyde contracting quadrol part are described; And N atom and Ti coordination can be from 3 on 3, the 5-di-tert-butyl salicylaldehyde contracting quadrol part, in the 5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex-and CH=N-CH
2-CH
2-the proton absorption peak from δ=8.431ppm move to δ=8.518ppm and-CH=N-C
H 2The doublet that the splitting of-proton absorption peak becomes two peak areas to equate obtains proof.Behind N atom and the Ti Atomic coordinate, make the cloud density of N atom reduce, adjacent with the N atom-CH
2-on the H atom because the effect of deshielding, split and be divided into the two symmetrical groups peak.Compare with part, the chemical shift of corresponding proton peak is all shifted to low in the title complex hydrogen spectrum.The above results shows that after part and titanium coordination, corresponding H proton deshielding effect enhancing causes low of its chemical shift picture mobile.The final product that is made by above-mentioned analysis explanation present embodiment 1-6 is for being 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.
Operational condition and method: under the room temperature, use through the Mo of graphite monochromatization Ka ray (l=0.071073 nm), scan mode is φ-w, and intensity data has carried out LP correction, experience absorption correction, structure elucidation and refine SHELXTL97 program.Instrument: AFC10/Saturn724+ ray single crystal diffractometer.
The molecular structural formula of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex crystal is C
71H
100O
6N
4Ti
2, molecular weight M=1201.35 belongs to triclinic(crystalline)system, and spacer is C2/c, unit cell parameters Z=4, a=25.495 (8), b=16189 (4), c=17.599 (5), α=90 °, β=110.209 (3) °, γ=90 °, V=6801 (3)
3(seeing Fig. 4 for details).Relevant main bond distance and bond angle such as table 1 with the Ti atom.
Table 1 relevant main bond distance and bond angle with the Ti atom
| Bond lengths ( ? ) | ? | ? | ? |
| Ti(1)-O(1) | 1.976(2) | Ti(1)-N(1) | 2.187(3) |
| Ti(1)-O(2) | 1.885(2) | Ti(1)-N(2) | 2.269(2) |
| Ti(1)-O(3) | 1.870(2) | O(1)-C(1) | 1.327(3) |
| Ti(1)-O(3)A | 1.832(2) | O(2)-C(16) | 1.339(3) |
| Angles ( ° ) | ? | ? | ? |
| O(3)A-Ti(1)-O(3) | 81.56(9) | O(2)-Ti(1)-O(1) | 97.83(9) |
| O(3)A-Ti(1)-O(1) | 88.22(9) | O(3)A-Ti(1)-N(1) | 109.97(9) |
| O(1)-Ti(1)-N(1) | 77.99(9) | O(3)-Ti(1)-N(1) | 81.85(9) |
| N(1)-Ti(1)-N(2) | 71.85(9) | O(2)-Ti(1)-N(1) | 148.12(9) |
| O(2)-Ti(1)-N(2) | 79.91(9) | O(3)A-Ti(1)-N(2) | 162.95(9) |
| O(3)-Ti(1)-O(2) | 108.93(9) | Ti(1)A-O(3)-Ti(1) | 98.32(9) |
| O(3)-Ti(1)-N(2) | 81.96(9) | O(1)-Ti(1)-N(2) | 108.55(9) |
| O(3)-Ti(1)-O(1) | 152.72(9) | O(3)A-Ti(1)-Ti(1)A | 41.35(6) |
| O(3)-Ti(1)-Ti(1)A | 40.32(6) | O(2)-Ti(1)-Ti(1)A | 112.59(6) |
| O(1)-Ti(1)-Ti(1)A | 123.66(6) | N(1)-Ti(1)-Ti(1)A | 95.17(6) |
| N(2)-Ti(1)-Ti(1)A | 122.28(7) | ? | ? |
Operational condition: argon atmosphere, 10 ℃/min of temperature rise rate.Instrument: STA 449C structural synthesis thermal analyzer (Germany, NETSCH company).
As can be seen, 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex has two weightless temperature districts from the TG curve of Fig. 5.The temperature range of the first step thermolysis is 150 ~ 180 ℃, sample is 7.72% at this interval rate of weight loss, contain toluene in the sample as can be known by nmr analysis and single crystal diffraction result, if what lose is toluene, so theoretical rate of weight loss should be 7.66%, this and measured value are almost equal, therefore infer between this resolver it is the process that loses toluene in the sample; The second step decomposition temperature interval is 360 ~ 400 ℃, is the last decomposition course of 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex.The temperature of first endotherm(ic)peak correspondence is about 160 ℃ on the DSC curve, and the temperature of second endotherm(ic)peak correspondence is about 400 ℃, and these two peaks are respectively to two decomposition coursees of the TG curve of Fig. 6.
The 4th part 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is at preparation D, and the ring-opening polymerization of L-rac-Lactide becomes Application of Catalyst in the poly(lactic acid)
Such title complex all is to insert the catalysis that mechanism is carried out according to coordination.What play katalysis mainly is oxygen on atoms metal and the O-Ti key.
4 clean ampoules are toasted 3 hours in 180 ℃ retort furnace after, nitrogen is driven the air in the ampoule out of, each ampoule takes by weighing the D of about 3 grams, the L-rac-Lactide, according to D, the mixed that the mol ratio of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is respectively 2300:1,2600:1,2800:1,3000:1 is even, vacuumize, envelope is molten.Melt polymerization is 16 hours in 160 ℃ oil bath, after polymerization finishes, takes out ampoule and is cooled to room temperature, reaction product is dissolved in the methylene dichloride, drip and extract the poly(lactic acid) that generates in dehydrated alcohol, vacuum-drying is measured polylactic acid molecule amount and molecular weight dispersity to constant weight.Work as D, when the mol ratio of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex was 2600:1, gained polylactic acid molecule amount was 9.058 * 10 to the maximum
4G/mol, molecular weight dispersity are 1.16.The chemical formula of described poly(lactic acid) is
, wherein, according to the highest and minimum average molecular weight of poly(lactic acid) in the following form divided by poly lactic acid polymerized unit, n=1217 ~ 1259.
| Monomer/catalyst (mol ratio) | Mn（×10 4） | PDI |
| 2300:1 | 8.980 | 1.21 |
| 2600:1 | 9.058 | 1.16 |
| 2800:1 | 8.973 | 1.14 |
| 3000:1 | 8.762 | 1.09 |
4 clean ampoules are toasted 3 hours in 180 ℃ retort furnace after, nitrogen is driven the air in the ampoule out of, each ampoule takes by weighing the D of about 3 grams, the L-rac-Lactide, according to D, the mixed of the mol ratio 2600:1 of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is even, vacuumize, envelope is molten.Respectively at melt polymerization in 150 ℃, 160 ℃, 170 ℃, 180 ℃ the oil bath 16 hours, after polymerization finishes, take out ampoule and be cooled to room temperature, reaction product is dissolved in the methylene dichloride, drip and in dehydrated alcohol, extract the poly(lactic acid) that generates, vacuum-drying is measured polymericular weight and molecular weight dispersity to constant weight.When temperature of reaction was 160 ℃, gained polylactic acid molecule amount was 9.058 * 10 to the maximum
4G/mol, molecular weight dispersity are 1.16.The chemical formula of described poly(lactic acid) is
, wherein, come n=1199 ~ 1259 according to poly(lactic acid) in the following form is the highest divided by poly lactic acid polymerized unit with the minimum average molecular weight.
| Temperature of reaction (℃) | Mn（×10 4） | PDI |
| 150 | 8.910 | 1.13 |
| 160 | 9.058 | 1.16 |
| 170 | 8.810 | 1.20 |
| 180 | 8.627 | 1.21 |
4 clean ampoules are toasted 3 hours in 180 ℃ retort furnace after, nitrogen is driven the air in the ampoule out of, each ampoule takes by weighing the D of about 3 grams, the L-rac-Lactide, according to D, the mixed of the mol ratio 2600:1 of L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium is even, vacuumize, envelope is molten.Respectively melt polymerization 6,12,16,20 hours in 160 ℃ oil bath, after polymerization finishes, take out ampoule and be cooled to room temperature, reaction product is dissolved in the methylene dichloride, drip and in dehydrated alcohol, extract the poly(lactic acid) that generates, vacuum-drying is measured polymericular weight and molecular weight dispersity to constant weight.When reacting 16 hours, gained polylactic acid molecule amount is 9.058 * 10 to the maximum
4G/mol, molecular weight dispersity are 1.16.The chemical formula of described poly(lactic acid) is
, wherein according to the highest and minimum average molecular weight of poly(lactic acid) in the following form divided by poly lactic acid polymerized unit, n=1238 ~ 1280.
| Reaction times (h) | Mn（×10 4） | |
| 6 | 8.912 | 1.12 |
| 12 | 8.960 | 1.15 |
| 16 | 9.058 | 1.16 |
| 20 | 9.210 | 1.24 |
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (2)
1. use 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex to prepare the method for poly(lactic acid), it is characterized in that: with D, L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex be at mol ratio 2300-3000:1, under 150-180 ℃, reacted 6-20 hour, and got poly(lactic acid); Described 3, the structural formula of 5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex is shown in I:
T-Bu is the tertiary butyl in the structural formula.
2. method according to claim 1 is characterized in that: with D, L-rac-Lactide and 3,5-di-tert-butyl salicylaldehyde contracting quadrol titanium complex be at mol ratio 2600:1, under 160 ℃, reacted 16 hours, gets poly(lactic acid).
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| US20050192454A1 (en) * | 2000-08-02 | 2005-09-01 | Nesmeyanov Institute Of Organoelement Compounds And King's College London | Process for the cyanation aldehydes |
| CN101659628A (en) * | 2009-09-09 | 2010-03-03 | 重庆大学 | Titanium complex, preparation method and use thereof |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050192454A1 (en) * | 2000-08-02 | 2005-09-01 | Nesmeyanov Institute Of Organoelement Compounds And King's College London | Process for the cyanation aldehydes |
| CN101659628A (en) * | 2009-09-09 | 2010-03-03 | 重庆大学 | Titanium complex, preparation method and use thereof |
Non-Patent Citations (12)
| Title |
|---|
| A practical Ti-salen catalyst based on dimeric salen ligand for asymmetric addition of trimethylsilyl cyanide to aldehydes;Chenwei Lv等,;《Catalysis Communications》;20110423;第12卷(第13期);第1242-1245页, 尤其是第1243页图2、第1243页方案1和2.3部分 * |
| Asymmetric cyanohydrin synthesis using heterobimetallic catalysts obtained from titanium and vanadium complexes of chiral and achiral salen ligands;Yuri N. Belokon等,;《Tetrahedron》;20070711;第63卷(第24期);第5287-5299页, 尤其是第5288页方案1和第5289页图3 * |
| Asymmetric cyanohydrin synthesis using heterobimetallic catalysts obtained from titanium and vanadium complexes;Yuri N. Belokon等,;《Tetrahedron》;20070711;第63卷(第24期);第5287-5299页, 尤其是第5288页方案1和第5296-5297页4.2和4.3部分 * |
| Charlotte K. A. Gregson等,.Titanium–salen complexes as initiators for the ring opening polymerisation of rac-lactide.《Dalton Trans.》.2006,(第25期),第3134-3140页, 尤其是第3135页方案1、图2和第3136页表2. |
| Chenwei Lv等,.A practical Ti-salen catalyst based on dimeric salen ligand for asymmetric addition of trimethylsilyl cyanide to aldehydes.《Catalysis Communications》.2011,第12卷(第13期),第1242-1245页, 尤其是第1243页图2、第1243页方案1和2.3部分. |
| In situ formation of heterobimetallic salen complexes containing titanium and/or vanadium ions;Yuri N. Belokon等,;《Inorganic Chemistry》;20080409;第47卷(第9期);第3801-3814页, 尤其是第3803页Scheme 2 * |
| Study on Mn(III)-salen and catalysis for styrene oxidation;Zhang Zhang等,;《Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry》;20080612;第38卷(第4期);第352-355页, 尤其是第352页2.2.1部分和第353页方案1 * |
| Titanium–salen complexes as initiators for the ring opening polymerisation of rac-lactide;Charlotte K. A. Gregson等,;《Dalton Trans.》;20060327(第25期);第3134-3140页, 尤其是第3135页方案1、图2和第3136页表2 * |
| Yuri N. Belokon等,.Asymmetric cyanohydrin synthesis using heterobimetallic catalysts obtained from titanium and vanadium complexes of chiral and achiral salen ligands.《Tetrahedron》.2007,第63卷(第24期),第5287-5299页, 尤其是第5288页方案1和第5289页图3. |
| Yuri N. Belokon等,.Asymmetric cyanohydrin synthesis using heterobimetallic catalysts obtained from titanium and vanadium complexes.《Tetrahedron》.2007,第63卷(第24期),第5287-5299页, 尤其是第5288页方案1和. |
| Yuri N. Belokon等,.In situ formation of heterobimetallic salen complexes containing titanium and/or vanadium ions.《Inorganic Chemistry》.2008,第47卷(第9期),第3801-3814页, 尤其是第3803页Scheme 2. |
| ZhangZhang等 .Study on Mn(III)-salen and catalysis for styrene oxidation.《Synthesis and Reactivity in Inorganic |
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