CN104530392B - A kind of preparation method of polylactide - Google Patents
A kind of preparation method of polylactide Download PDFInfo
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Abstract
The preparation method that the invention discloses polylactide, comprises the following steps: catalyst, organic solvent and lactide is mixed, carries out ring-opening polymerization, undertaken processing to obtain polylactide by reactant after reaction under anhydrous and oxygen-free and inert gas shielding；Described catalyst is amido anilino-lithium compound.The present invention is with amido anilino-lithium compound for catalyst, and reaction controllability is good, mild condition, and reaction rate is fast, does not need to add alcohol promoter and polyreaction can occur, and catalysis activity is high, and the polylactide molecular weight obtained is controlled, productivity is high, metal residual is few.Additionally, polymerization technology of the present invention is simple, common solution polymerization process can be adopted, by the control of polymeric reaction condition, it is possible to the molecular weight of regulation and control polymer, selectivity is wide, and the molecular weight distribution that obtains is narrow, has excellent physicochemical property, it is possible to meet the needs in market.
Description
Technical field
The present invention relates to a kind of amido anilino-lithium compound and preparation method thereof, further relate to the method using this amido anilino-lithium compound as catalyst preparing polylactide.
Background technology
Our life has been changed with the birth of macromolecular material that oil is raw material, each corner of our daily life of diversified high performance polymer material ubiquity, unprecedented convenience is brought to our life, but alarming it is, under the background of Global Oil growing tension, the fast development of the macromolecular material relying on petroleum is subject to severely restricts.And, macromolecule polymeric material is difficult to degrade, and substantial amounts of macromolecule polymeric material garbage accumulates in the pollution in actual life, environment for human survival caused for a long time also to be increased the weight of gradually.Conventional polymer material faces two hang-ups of energy crisis and environmental pollution, finds the Renewable resource replacing oil, development environment friendly, biodegradation type new material become the trend of following macromolecule polymeric material development.
Polylactone is as the macromolecular material that the macromolecule polyalcohol of biodegradable is the most noticeable environmental type.In natural living environment, discarded polylactone material can be resolved into water and carbon dioxide thoroughly by the microorganism in soil, environmental protection and renewable.Because polylactone is nontoxic, nonirritant, and has good biocompatibility, therefore it is widely used in medical science and field of Environment Protection, for instance operation suture thread, packaging, drug controlled release and tissue engineering bracket etc..The performance that the excellent biocompatibility of polylactone, biological degradability and sustainable development utilize so that it is have become as 21 century most promising macromolecular material.
Mostly polylactone is to be obtained by its corresponding cyclic lactone ring-opening polymerisation, and polyreaction needs to carry out in the presence of a catalyst.Mostly catalyst conventional at present is the coordination compound that part and metal are formed, and the metal in catalyst includes magnesium, calcium, germanium, stannum, aluminum, zinc, ferrum, titanium, zirconium, group of the lanthanides etc..Selecting of catalyst is all very crucial for the performance of the speed of ring-opening polymerization, products obtained therefrom, therefore studies the good catalyst of new performance very necessary.
Summary of the invention
The preparation method that the invention provides a kind of polylactide, the method is simple to operate, and with amido anilino-lithium compound for catalyst, reaction rate is fast, and mild condition, products therefrom productivity height, 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, it is preferred to 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyls；
。
In above-claimed cpd, gained compound is simple and easy to get, can be seen that from structural formula, the lithium being connected with a part forms bridge crosslinking structure with another part, when as catalyst, so it is more beneficial for monomer carries out coordination insertion, catalytic effect is better, also can be rapidly performed by polyreaction under not having alcohol auxiliary agent.
This amido anilino-lithium compound preparation method comprise the following steps: amido anilino-part is added in organic solvent, then-10～30oAdd lithium alkylide under C, make nature rise to room temperature after adding and react, filter after reaction, wash, obtain amido anilino-lithium compound.
Amido anilino-part is as follows with the equation that lithium alkylide reacts, and wherein the structural formula of amido anilino-part is such as shown in formula A, and Ar is the aryl replaced, it is preferred to 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyls:
In above-mentioned preparation method, amido anilino-part used has had relevant report in the prior art, patent ZL201210184308.7 such as, describes the synthetic method of this part, such as document (Gao Aihong again, novel aluminum, zinc, the synthesis of chromium metal complex, sign and catalytic Quality Research, China's Ph.D. Dissertation's full-text database) in also disclose that and be not described in detail in this synthetic method of this part.
In above-mentioned preparation method, described lithium alkylide is preferably lithium methide or n-BuLi.
In above-mentioned preparation method, mol ratio 1:1～1.3 of amido anilino-part and lithium alkylide, it is preferable that 1:1～1.05.
In above-mentioned preparation method, described organic solvent is one or both in hexane, toluene and hexamethylene, it is preferred to hexane or hexamethylene.
In above-mentioned preparation method, consumption of organic solvent is 5～40 times of reaction raw materials (part and lithium alkylide) gross mass.
In above-mentioned preparation method, reaction carries out under inert gas shielding.
In above-mentioned preparation method, lithium alkylide is preferably in-10～0oAdd 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, it is preferable that 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 serve as lactide ring-opening polymerisation and prepares the catalyst of polylactide, shown in the structural formula of described lactide such as formula (III):
。
The preparation method of polylactide specifically includes following steps: amido anilino-lithium compound catalyst, organic solvent, alcohol promoter (if any) and lactide are mixed; under anhydrous and oxygen-free and inert gas shielding, carry out ring-opening polymerization, undertaken processing to obtain polylactide by reactant after reaction.
In above-mentioned ring-opening polymerization, the mol ratio of lactide and amido anilino-Al catalysts is 30～2000:1.
In said method, reaction organic solvent used is toluene or oxolane, it is preferable that toluene.
In said method, polymeric reaction temperature is 20～130 DEG C.
In said method, polymerization reaction time can select within the scope of 1-1440 minute.
In said method, alcohol promoter is benzylalcohol or isopropanol.
In said method, when using alcohol promoter, the mol ratio of alcohol promoter and catalyst is 1～3:1.
In said method, the process that reactant is carried out adds water after referring to reaction and terminates reaction, precipitates with ethanol, and for several times, ambient temperature in vacuum dries, and obtains polylactide in washing.
The present invention carries out lactide ring-opening polymerization using amido anilino-lithium compound as catalyst, the polylactide narrow molecular weight distribution being obtained by reacting, and the molecular weight obtaining product is controlled, and productivity is high, and metal residual is few.
Catalysis activity when amido anilino-lithium compound of the present invention is as ring-opening polymerization catalyst is high, when general metal complex is as catalyst, it is required for the catalysis activity that competence exertion is high under the auxiliary of alcohol promoter, but catalyst of the present invention is not having alcohol promoter to deposit still can to have in case significantly high catalysis activity, without influence on the carrying out of ring-opening polymerization, the polymer obtained is the polymer not terminated.Certainly, catalyst of the present invention can also carry out catalyzed ring opening polymerization under alcohol promoter exists, now the product of gained and the structure being not added with alcohol promoter and being 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 changes various, the active height of catalysis, safety non-toxic, the ring-opening polymerization of the efficient catalyzing lactone of energy and lactide, can be widely applied to cyclic lactone ring-opening polymerisation, be a kind of very good catalyst.
Ring lactide of the present invention is obtained by lactide ring-opening polymerisation, with amido anilino-lithium compound for catalyst during preparation, reaction controllability is good, mild condition, reaction rate is fast, not needing to add alcohol promoter and polyreaction can occur, catalysis activity is high, and the polylactide molecular weight obtained is controlled, productivity is high, metal residual is few.Additionally, polymerization technology of the present invention is simple, common solution polymerization process can be adopted, by the control of polymeric reaction condition, it is possible to the molecular weight of regulation and control polymer, selectivity is wide, and the molecular weight distribution that obtains is narrow, has excellent physicochemical property, it is possible to meet the needs in market.
Accompanying drawing explanation
Fig. 1 is the crystal structure figure of embodiment 3 products obtained therefrom.
Detailed description of the invention
Further illustrating the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain is shown in claim.
In following embodiment, amido anilino-part used prepares according to existing method, does not repeat them here.
Prepare amido aniline lithium compound (I)
Amido aniline lithium compound is to be reacted, by part and lithium alkylide, the coordination compound generated, and the compound that different ligands is obtained, such as shown in following formula A, is illustrated by the structural formula of its part below.
Embodiment 1
Ligand structure formula such as above formula (A) used, wherein Ar is 4-aminomethyl phenyl, course of reaction is: in a nitrogen atmosphere, part 0.51g is dissolved in the dry normal hexane of 10mL, at-10 DEG C, add the n-BuLi of equimolar amounts, be slowly raised to room temperature reaction 3 hours, filter and with dry normal hexane filter wash cake, collect and dry and be weighed as 0.49g solid, productivity 94%.
Products therefrom nuclear-magnetism information is as follows, from nuclear-magnetism information it can be seen that the lithium compound that Ar is 4-aminomethyl phenyl synthesizes successfully.
1HNMR(400MHz,CDCl3)δ7.40(d,J=7.5Hz,2H,Ph-H),7.24–6.91(m,10H,Ph-H),6.62(d,J=7.6Hz,2H,Ph-H),4.40(s,4H,CH 2N),2.72(s,12H,NCH 3),2.20(s,6H,CH 3)。
13CNMR(100MHz,CDCl3)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 such as above formula (A) used, wherein Ar is 2,6-3,5-dimethylphenyl, course of reaction is: under nitrogen atmosphere, is dissolved in by part 0.47g in the dry hexamethylene of 10mL, adds the n-BuLi of 1.05 times of moles at 0 DEG C, it is slowly raised to room temperature reaction 6 hours, filter and use dry normal hexane filter wash cake, collecting and dry weighing obtains 0.46g solid, productivity 95%.
Products therefrom nuclear-magnetism information is as follows, from nuclear-magnetism information it can be seen that the lithium compound that Ar is 2,6-3,5-dimethylphenyls synthesizes successfully.
1HNMR(400MHz,CDCl3)δ7.42(dd,J=6.2,1.3Hz,2H,Ph-H),7.28-7.25(m,2H,Ph-H),7.17(dd,J=7.0,1.0Hz,2H,Ph-H),7.06(td,J=7.4,1.2Hz,2H),7.00(d,J=7.4Hz,4H),6.83(t,J=7.5Hz,2H),4.17(s,4H,NCH 2Ph),2.73(s,12H,NCH 3),2.31(s,12H,PhCH 3)。
13CNMR(100MHz,CDCl3)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 such as above formula (A) used, wherein Ar is 2,6-diethyl phenyl, course of reaction is: under nitrogen atmosphere, is dissolved in 5mL dry toluene by part 0.34g, adds the lithium methide of 1.1 times of moles at-10 DEG C, it is raised to room temperature reaction 1 hour, filter and use dry normal hexane filter wash cake, collecting and the dry 0.32g that weighs to obtain, productivity 91%.
The crystal structure figure of products obtained therefrom, as it is shown in figure 1, nuclear-magnetism information is as follows, this shows that the lithium compound that Ar is 2,6-diethyl phenyl synthesizes successfully.
1HNMR(400MHz,CDCl3)δ7.48–7.45(m,2H,Ph-H),7.29(dd,J=7.8,1.5Hz,2H,Ph-H),7.19(dd,J=8.0,1.1Hz,2H,Ph-H),7.13(d,J=7.9Hz,2H,Ph-H),7.09(m,4H,Ph-H),6.97(dd,J=8.1,6.9Hz,2H,Ph-H),4.12(s,4H,NCH 2Ph),2.73(s,12H,NCH 3),2.52(q,J=7.5Hz,8H,CH 2CH3),1.15(t,J=7.5Hz,12H,CH2CH 3)。
13CNMR(100MHz,CDCl3)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 such as above formula (A) used, wherein Ar is 2,6-diisopropyl phenyl, course of reaction is: under nitrogen atmosphere, is dissolved in by part 0.46g in the dry normal hexane of 20mL, adds the n-BuLi of 1.05 times of moles at-5 DEG C, it is raised to room temperature reaction 12 hours, filter and use dry normal hexane filter wash cake, collecting and the dry 0.45g that weighs to obtain, productivity 96%.
Products therefrom nuclear-magnetism information is as follows, from nuclear-magnetism information it can be seen that the lithium compound that Ar is 2,6-diisopropyl phenyls synthesizes successfully.
1HNMR(400MHz,CDCl3)δ7.48(d,J=7.1Hz,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,NCH 2Ph),3.58–3.36(m,4H,CH(CH3)2),2.78(s,12H,NCH 3),1.33(d,J=6.5Hz,12HCH(CH 3)2)。
13CNMR(101MHz,CDCl3)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 such as above formula (A) used, wherein Ar is 2,6-diethyl phenyl, course of reaction is: under nitrogen atmosphere, is dissolved in 5mL dry toluene by part 0.34g, adds the lithium methide of 1.05 times of moles at-5 DEG C, it is raised to room temperature reaction 3 hours, filter and use dry normal hexane filter wash cake, collecting and the dry 0.33g that weighs to obtain, productivity 96%.
Embodiment 6
Ligand structure formula such as above formula (A) used, wherein Ar is 2,6-diethyl phenyl, course of reaction is: under nitrogen atmosphere, is dissolved in 5mL dry toluene by part 0.34g, adds the lithium methide of 1.3 times of moles at 30 DEG C, it is raised to room temperature reaction 12 hours, filter and use dry normal hexane filter wash cake, collecting and the dry 0.30g that weighs to obtain, productivity 87%.
Prepare polylactide
Embodiment 7
Reacting under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing, 20 μm of olAr of order addition are the lactide of the catalyst of 4-aminomethyl phenyl, 30mL toluene and 20mmol, are subsequently placed in 80oIn the oil bath of C, adding a small amount of water and terminate reaction after reacting 4 hours, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 2.80 grams, productivity 97.1%, molecular weight 18.7 ten thousand.
Embodiment 8
Reacting under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing, 20 μm of olAr of order addition are the lactide of the catalyst of 4-aminomethyl phenyl, 30mL toluene, 20 μm of ol benzylalcohols and 20mmol, are subsequently placed in 80oIn the oil bath of C, adding a small amount of water and terminate reaction after reacting 4 hours, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 2.75 grams, productivity 95.3%, molecular weight 16.4 ten thousand.
Embodiment 9
Reacting under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing, 20 μm of olAr of order addition are the lactide of the catalyst of 4-aminomethyl phenyl, 30mL toluene and 20mmol, are subsequently placed in 80oIn the oil bath of C, adding a small amount of water and terminate reaction after reacting 8 hours, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 2.86 grams, productivity 99.2%, molecular weight 20.1 ten thousand.
Embodiment 10
Reacting under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing, 20 μm of olAr of order addition are the lactide of the catalyst of 4-aminomethyl phenyl, 30mL toluene and 20mmol, are subsequently placed in 80oIn the oil bath of C, adding a small amount of water and terminate reaction after reacting 1 hour, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 2.64 grams, productivity 83.2%, molecular weight 12.4 ten thousand.
Embodiment 11
React under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing order add 30 μm of olAr be that 2.6-diethylbenzene is catalyst based, the lactide of 60mL toluene and 60mmol, be subsequently placed in 70oIn C oil bath, adding a small amount of water and terminate reaction after reacting 12 hours, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 8.53 grams, molecular weight 38.6 ten thousand, yield 98.6%.
Embodiment 12
React under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing order add 1000 μm of olAr be that 2.6-dimethyl benzene is catalyst based, the lactide of 70mL toluene and 30mmol, be subsequently placed in 70oIn C oil bath, adding a small amount of water and terminate reaction after reacting 1 hour, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 4.16 grams, molecular weight 1.3 ten thousand, yield 96.1%.
Embodiment 13
React under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing order add 20 μm of olAr be that 2.6-diisopropyl benzene is catalyst based, the lactide of 30mL toluene and 10mmol, be subsequently placed in 110oIn C oil bath, adding a small amount of water and terminate reaction after reacting 1 hour, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 1.33 grams, molecular weight 10.4 ten thousand, yield 92.1%.
Embodiment 14
React under anhydrous and oxygen-free and inert gas shielding; first in the ampulla after toasting with high pure nitrogen gas washing order add 10 μm of olAr be that 2.6-dimethyl benzene is catalyst based, the lactide of 30mL toluene, 20 μm of ol isopropanols and 20mmol, be subsequently placed in 50oIn C oil bath, adding a small amount of water and terminate reaction after reacting 7 hours, precipitate with ethanol, wash for several times, ambient temperature in vacuum dries, and obtains 2.81 grams, molecular weight 10.4 ten thousand, yield 97.2%.
Embodiment 15
React under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing order add 20 μm of olAr be that 2.6-diethylbenzene is catalyst based, the lactide of 50mL toluene, 10 μm of ol isopropanols and 20mmol, then 20oC adds a small amount of water and terminates reaction after reacting 12 hours, precipitate with ethanol, wash for several times, and ambient temperature in vacuum dries, and obtains 2.57 grams, molecular weight 28.3 ten thousand, yield 89.1%.
Embodiment 16
React under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after toasting with high pure nitrogen gas washing order add 20 μm of olAr be that 2.6-diethylbenzene is catalyst based, the lactide of 50mL toluene and 20mmol, then 20oC adds a small amount of water and terminates reaction after reacting 12 hours, precipitate with ethanol, wash for several times, and ambient temperature in vacuum dries, and obtains 2.76 grams, molecular weight 17.9 ten thousand, yield 95.7%.
Comparative example
Preparing Ar according to the method for embodiment 1 in patent 201210184308.7 is 4-aminomethyl phenyl, R1For methyl, R2For the Amido aniline group zinc compound of ethyl, structural formula is as follows:
The method identical with embodiment 7 is adopted to prepare polylactide, the difference is that: catalyst used is the Amido aniline group zinc compound of this identical substituent group, in 80oIn C oil bath, reaction adds a small amount of water and terminates reaction after increasing to 12 hours, precipitate with ethanol, wash for several times, and ambient temperature in vacuum dries, and obtains 0.24 gram, molecular weight 1.1 ten thousand, yield 8.2%.From the results, it was seen that this kind of catalyst be just to increase the response time also could not the polyreaction of catalysis lactide smoothly.
Claims (11)
1. a preparation method for polylactide, is characterized in that comprising the following steps: catalyst, organic solvent and lactide is mixed, carries out ring-opening polymerization, undertaken processing to obtain polylactide by reactant after reaction under anhydrous and oxygen-free and inert gas shielding；Described catalyst is amido anilino-lithium compound, and shown in the following formula I of its structural formula, in formula, Ar is 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyls；
。
2. preparation method according to claim 1, is characterized in that: method for preparing catalyst is: added by amido anilino-part in organic solvent, then-10～30oAdd 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 such as shown in following formula A, and wherein Ar is the aryl replaced:
。
3. preparation method according to claim 2, is characterized in that: described lithium alkylide is lithium methide or n-BuLi；Mol ratio 1:1～1.3 of amido anilino-part and lithium alkylide.
4. preparation method according to claim 3, is characterized in that: mol ratio 1:1～1.05 of amido anilino-part and lithium alkylide.
5. preparation method according to claim 2, is characterized in that: described organic solvent is one or both in hexane, toluene and hexamethylene；Reaction carries out under inert gas shielding.
6. preparation method according to claim 2, is characterized in that: lithium alkylide is-10～0oAdd under C in the mixture of amido anilino-part and organic solvent；The room temperature reaction time is 1～12 hour.
7. preparation method according to claim 6, is characterized in that: the room temperature reaction time is 3～6 hours.
8. preparation method according to claim 1, is characterized in that: the mol ratio of lactide and catalyst is 30～2000:1.
9. preparation method according to claim 1, is characterized in that: described organic solvent is toluene or oxolane；Reaction temperature is 20～110 DEG C；Response time is 1-1440 minute.
10. the preparation method according to claim 1,8 or 9, is characterized in that: the mol ratio also including alcohol promoter, alcohol promoter and catalyst is 0.5～2:1.
11. preparation method according to claim 10, it is characterized in that: described alcohol promoter is benzylalcohol or isopropanol.
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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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