CN110204697A - The method for preparing L- lactide and 6-caprolactone random copolymer - Google Patents
The method for preparing L- lactide and 6-caprolactone random copolymer Download PDFInfo
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- CN110204697A CN110204697A CN201910553504.9A CN201910553504A CN110204697A CN 110204697 A CN110204697 A CN 110204697A CN 201910553504 A CN201910553504 A CN 201910553504A CN 110204697 A CN110204697 A CN 110204697A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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Abstract
The method that the present invention obtains complete random copolymer about L- lactide and 6-caprolactone " treating different things alike ", key step is as follows: L- lactide and 6-caprolactone are under the catalytic action of metal complex, 30-60 DEG C of open loop realization copolymerization in organic solvent, obtains the random copolymer of the two；Wherein, catalyst is the stable rare earth metal alkoxy of the bis aryloxy ligand of schiff bases bridging, aryloxide complexes, and structural formula is as follows:The catalyst structure that the present invention uses is clear, and synthetic method is simple, and post-processes simply, and yield is very high；Copolyreaction is raw materials used simple and easy to get, and reaction condition is very mild, easy to operate.Gained copolymer is height random copolymer, compensates for defect existing for respective homopolymer, the two advantage is combined so that the copolymer can satisfy a variety of industry, life requirement.In addition, catalyst amount is small, to realize that large-scale industrial production provides possibility.
Description
Technical field
The present invention relates to the preparation technical field of polymer more particularly to a kind of prepare L- lactide and 6-caprolactone height
The method of random copolymer.
Background technique
Poly L-lactide (PLLA) and some critical natures of poly-epsilon-caprolactone (PCL) in medicine and pharmaceutical applications by
Pay attention to extensively.Meanwhile they are functionally complementary in some mechanical performances.PLLA does not have infiltration to most of drug
Property, half-life period in vivo only have several weeks.PCL has a good permeability to the drug of some low molecular weights, but it
Long half time was up to 1 year in vivo.And the copolymer of L- lactide and 6-caprolactone can combine the two,
Achieve the effect that advantage and disadvantage complementation, obtains the high molecular material with good osmotic effect and shorter degradation time, preferably
Meet industrial requirement.It is total to currently, the copolyreaction that various catalyst are used to be catalyzed L- lactide and 6-caprolactone is obtained block
The example of polymers and gradient copolymer has very much, but obtains a kind of catalyst of copolymer that height is random at normal temperature almost
Do not report.The relevant technologies are mainly as follows:
2010, Nomura et al. selected gem-dimethyl bridging Salen aluminium benzyloxy complex as catalyst, at 90 DEG C
Lactide and caprolactone copolymerization are catalyzed in toluene, reaction 10h latter two monomer has obtained random copolymer close to conversion completely,
But the System Catalyst dosage is higher, need 2~3mol%, temperature it is also higher (referring to N.Nomura, A.Akita,
R.Ishii and M.Mizuno,J.Am.Chem.Soc.2010,132,1750–1751)。
2012, Pellecchia et al. selected asymmetric diamine base aluminium methyl complex as catalyst, first at 70 DEG C
4 days two kinds of monomers are reacted in benzene and convert about half, have obtained random copolymer.Although reaction temperature decreases, urge
Agent reactivity it is too low (referring to G.Li, M.Lamberti, D.Pappalardo and C.Pellecchia,
Macromolecules 2012,45,8614-8620)。
The same year, Ma Haiyan et al. select the double aluminium methyl complexs of the amido bridged linkage bis aryloxy of different substituents as catalysis
Agent adjusts the reactivity ratio of L- lactide and 6-caprolactone by increasing temperature.Two kinds of monomer reactivity ratios are suitable at 130 DEG C, obtain
Atactic polymer.But in this system, it is too high to obtain random copolymer required temperature, once reduction temperature, then can only
Obtain block, gradual change and gradient copolymer (referring to Y.Wang, H.Ma, Chem.Commun.2012,48,6729-6731).
It 2016, is somebody's turn to do et al. and to select big steric hindrance monokaryon, double-core aluminum complex as catalyst, it is available under toluene high temperature to be randomly total to
Polymers.Reaction temperature needed for the system is up to 110 DEG C of disadvantages for becoming the catalyst (referring to C.Kan, H.Ma, RSC
Adv.2016,6,47402–47409)。
2014, Cui Dongmei et al. selected m-phenylene diamine (MPD) bridging Salan and Salen type aluminium methyl complex as catalysis
Agent is catalyzed the copolymerization of L- lactide and 6-caprolactone, obtains the product very close to random copolymer, but catalyst activity is inclined
Low (referring to: L.Li, B.Liu, D.Liu, C.Wu, S.Li, B.Liu, D.Cu, Organometallics 2014,33,6474-
6480)。
2017, it was catalyst, 70 DEG C of Toluenes that Visseaux et al., which selects the allyl rare earth metal complex of mixture,
In available random copolymer, but need to be added chain transfer agents in the reaction system, and the reaction time up to for 24 hours (ginseng
See: S.Fadlallah, J.Jothieswaran, F.Capet, F.Bonnet, M.Visseaux, Chem.Eur.J.2017,23,
15644–15654)。
2018, Yao Yingming et al. selected ethylenediamine base bridged linkage bis aryloxy rare earth metal complex as catalyst, and 90
It is reacted at DEG C and the random copolymer of L- lactide and 6-caprolactone, randomization degree (%): L- is obtained by transesterification process for 24 hours
LA- ε-CL chain link: ε-CL- ε-CL chain link=74:26.But the necessary method of fractional steps of the reaction carries out, according to the side of " treating different things alike "
Method or reduce reaction temperature then have to block copolymer (referring to H.Ouyang, K.Nie, D.Yuan, Y.Zhang,
D.Cui,Y.Yao,Sci.China Chem.2018,61,708-714.)。
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide it is a kind of prepare L- lactide and 6-caprolactone height without
The method for advising copolymer, this method are " treating different things alike " method, and the catalyst activity of selection is high, can be in item as mild as a dove
The copolyreaction of L- lactide and 6-caprolactone is catalyzed under part, gained copolymer is height random copolymer.
The present invention provides a kind of methods for preparing L- lactide and 6-caprolactone random copolymer, comprising the following steps:
Using L- lactide and 6-caprolactone as raw material, matched with the rare earth metal that the bis aryloxy ligand of schiff bases bridging is stable
Conjunction object is catalyst, and 30-60 DEG C occurs ring opening copolymer reaction in organic solvent, obtains L- lactide and 6-caprolactone randomly altogether
Polymers；The stable rare earth metal complex of the bis aryloxy ligand of the schiff bases bridging and L- lactide and 6-caprolactone rub
You are than being 1:120-500:120-500；The stable rare earth metal complex structure of the bis aryloxy ligand of the schiff bases bridging
Shown in formula such as formula (1) and/or formula (2):
Wherein THF is tetrahydrofuran molecule, R 2,6- di-t-butyl p-methylphenyl (C6H2-2,6-tBu2-4-CH3), tertiary fourth
Base (tBu), isopropyl (iPr), one kind of benzyl (Bn) and ethyl (Et).
Further, the preparation method of above-mentioned L- lactide and 6-caprolactone random copolymer specifically includes the following steps:
(1) the stable rare earth metal complex of the bis aryloxy ligand of schiff bases bridging is dissolved in organic solvent, is urged
Agent solution；Monomer L- lactide and 6-caprolactone are dissolved with organic solvent, it is molten to be added at one time above-mentioned catalyst thereto
Liquid reacts at 30-60 DEG C in confined conditions；
(2) terminator is added and terminates reaction, obtain L- lactide and 6-caprolactone random copolymer.
After step (2), with industrial alcohol settled polymer, for several times, vacuum oven pumps solvent and obtains filtration washing
The product of clean dry.
The structural formula of L- lactide (L-LA) and 6-caprolactone (ε-CL) difference is as follows:
Further, reaction time 2-7h.Preferably, reaction time 2-3h.
Further, the ratio of the catalyst and organic solvent is 2-5mmol:1mL.Preferably, the catalyst and
The ratio of organic solvent is 5mmol:1mL.
Further, catalyst, L-LA and ε-CL molar ratio be 1:120-500:120-500.Preferably, catalyst,
The molar ratio of L- lactide and 6-caprolactone is 1:120-300:120-300.
Further, organic solvent is one of toluene, n-hexane or tetrahydrofuran.
Further, in L-LA and ε-CL random copolymer, the content of L- lactide is 9-90%.
Further, in L-LA and ε-CL random copolymer, the content of 6-caprolactone is 10-91%.
In L-LA and ε-CL random copolymer, the catalyst when content of L-LA and ε-CL is by reaction, L- lactide and
The molar ratio of 6-caprolactone, the reaction time, reaction temperature and each substance charging sequence codetermined.
Further, further include the steps that terminator, which is added, terminates polymerization reaction.
Further, terminator is the hydrochloric acid solution or 95% ethanol water of ethyl alcohol.
In the present invention, the chemical general formula of the stable rare earth compound of the bis aryloxy ligand of schiff bases bridging is [LaL
(OR)(THF)n1]n2, L represents bridging schiff base ligand, L=NH [CH2CH2N=CH (2-O-3,5-tBu2C6H2)]2；THF is four
Hydrogen furans；R is 2,6- di-t-butyl p-methylphenyl, tert-butyl, isopropyl, benzyl or ethyl-；n1Represent tetrahydrofuran number, n1
=0 or 1；n2=1 or 2.
The present invention utilizes the ring opening copolymer of above-mentioned catalyst monomer L-LA and ε-CL, and the principle is as follows:
The reactivity ratio of the ring-opening polymerisation of both monomers of L-LA and ε-CL is suitable under polymerization initiating stage, the same terms
(rLA≈rCL≈1).It can prove that L-LA and ε-CL is almost started simultaneously in copolyreaction by the tracking to reaction process
Reaction, or even in preceding 7min, the conversion ratio of ε-CL is slightly greater than L-LA；With the progress of reaction, the conversion rate of L-LA is more than
ε-CL, and with the appearance of ester exchange reaction, until reaction terminates.Pass through1H NMR and13C NMR spectra tracking, it was demonstrated that shape
It is the equal coefficient result of reactivity ratio and ester exchange reaction of two kinds of one body approximations at height random copolymer.
According to the above aspect of the present invention, the present invention has at least the following advantages:
1) catalyst structure that the present invention uses is clear, and synthetic method is simple, and yield is high, isolates and purifies simple；
2) catalyst activity that the present invention selects is high, and catalyst amount is small, and the dosage of catalyst is reactant L-LA/ ε-
The 0.2-0.5mol% of CL, copolymer yield are high.When catalyst mole dosage is down to 0.2mol%, it is still able to maintain higher catalysis
Activity, less catalyst amount are that the purification of product provides convenience；
3) raw material is easy to get in preparation method disclosed by the invention；Reaction condition is very mild, it might even be possible at normal temperature
To height random copolymer；Reaction time is short, and the copolymer of different structure can be realized by changing the molar ratio of two kinds of monomers,
Operation and last handling process are simple, to realize that large-scale industrial production provides possibility.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is L- lactide and 6-caprolactone height random copolymer prepared in embodiment 3 in the section 4-5.5ppm
Nucleus magnetic hydrogen spectrum figure；
Fig. 2 is L- lactide and 6-caprolactone height random copolymer prepared in embodiment 3 in the area 169-174ppm
Between nucleus magnetic hydrogen spectrum figure.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
1 LaL (OC of embodiment6H2-2,6-tBu2-4-CH3) (THF) catalysis L-LA and ε-CL (molar ratio 50:50) combined polymerization
At height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2394g, 1.66mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1896g, 1.66mmol) is dissolved with 729 μ L toluene.Weigh R=C6H2-2,6-tBu2-4-CH3Metal Lanthanide complex
(10.6mg) is dissolved in the toluene of 1000 μ L, and the catalyst solution of 755 μ L (0.0083mmol) is taken to be added in polymerization bottle.60
It is transferred out of glove box after reacting 3h at DEG C, 60 μ L reaction solutions is taken out and carries out original position1HNMR characterization, then the ethyl alcohol of addition 95% is molten
Liquid terminates reaction, is settled with industrial alcohol, filters and multiple washing copolymer, is dried in vacuo 12h, obtain L- lactide and ε-oneself
Lactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=81:19.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=18.0 × 103G/mol, point
Son amount distribution PDI=1.99.
2 LaL (OC of embodiment6H2-2,6-tBu2-4-CH3) (THF) catalysis L-LA and ε-CL (molar ratio 50:50) combined polymerization
At height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2263g, 1.57mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1792g, 1.57mmol) is dissolved with 688 μ L toluene.Weigh R=C6H2-2,6-tBu2-4-CH3Metal Lanthanide complex
(10.6mg) is dissolved in the toluene of 1000 μ L, and the catalyst solution of 714 μ L (0.0078mmol) is taken to be added in polymerization bottle.30
It is transferred out of glove box after reacting 3h at DEG C, 60 μ L reaction solutions is taken out and carries out original position195% ethyl alcohol is then added in H NMR characterization
Solution terminates reaction, is settled with industrial alcohol, filters and multiple washing copolymer, vacuum drying 12h obtain L- lactide and ε-
Caprolactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=78:22.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=26.0 × 103G/mol, point
Son amount distribution PDI=2.23.
3 LaL (O of embodimenttBu) (THF) is catalyzed the height random copolymerization of L-LA and ε-CL (molar ratio 50:50) copolymerization
Object
Under the protection of glove box High Purity Nitrogen, L-LA (0.2475g, 1.72mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1960g, 1.72mmol) is dissolved with 805 μ L toluene.Weigh R=tThe metal Lanthanide complex (9.6mg) of Bu is dissolved in 1000 μ L
Toluene in, take the catalyst solution of 729 μ L (0.0086mmol) to be added in polymerization bottle.It is transferred out of after reacting 3h at 60 DEG C
Glove box takes out 60 μ L reaction solutions and carries out original position1HNMR characterization, the ethanol solution for being then added 95% terminates reaction, with industry
Alcohol sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymerization
Object.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=80:20.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=34.0 × 103G/mol, point
Son amount distribution PDI=2.06.
Embodiment 4LaL (OtBu) (THF) is catalyzed the height random copolymerization of L-LA and ε-CL (molar ratio 50:50) copolymerization
Object
Under the protection of glove box High Purity Nitrogen, L-LA (0.2139g, 1.48mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1694g, 1.48mmol) is dissolved with 687 μ L toluene.Weigh R=tThe metal Lanthanide complex (9.5mg) of Bu is dissolved in 1000 μ L
Toluene in, take the catalyst solution of 639 μ L (0.0074mmol) to be added in polymerization bottle.It is transferred out of after reacting 3h at 30 DEG C
Glove box takes out 60 μ L reaction solutions and carries out original position1H NMR characterization, the ethanol solution for being then added 95% terminates reaction, with industry
Alcohol sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymerization
Object.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=76:24.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=23.1 × 103G/mol, point
Son amount distribution PDI=2.03.
[LaL (the O of embodiment 5iPr)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2162g, 1.50mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1712g, 1.50mmol) is dissolved with 556 μ L toluene.Weigh R=iThe metal Lanthanide complex (7.0mg) of Pr is dissolved in 1000 μ L
Toluene in, take the catalyst solution of 784 μ L (0.0075mmol) to be added in polymerization bottle.It is transferred out of after reacting 3h at 60 DEG C
Glove box takes out 60 μ L reaction solutions and carries out original position1HNMR characterization, the ethanol solution for being then added 95% terminates reaction, with industry
Alcohol sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymerization
Object.
Find out from In situNMR figure (Fig. 1-2), for raw material without residue, L-LA and ε-CL conversion is complete；Randomization degree
(%): L-LA- ε-CL chain link: ε-CL- ε-CL chain link=80:20.Copolymer glass transition temperature: -6.4 DEG C, average chain
Length: LLA=0.84；LCL=1.15；Gpc analysis is carried out to obtained solid product, measures the M of copolymern=32.9 × 103g/
Mol, molecular weight distribution PDI=1.96.
[LaL (the O of embodiment 6iPr)]2It is catalyzed L-LA and ε-CL (molar ratio 40:60) copolymerization height random copolymer
L-LA (0.1730g, 1.20mmol) and 6-caprolactone (0.2055g, 1.80mmol) are taken, according to the side of embodiment 3
Method carries out polymerization reaction, obtains L-LA and ε-CL height random copolymer.Product manufactured in the present embodiment is characterized, as a result
It is as follows:
L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-CL- ε-CL chain link=67:33；
Copolymer glass transition temperature: -19.6 DEG C, Average Segment Length: LLA=0.59；LCL=1.31；To obtained solid product into
Row gpc analysis measures the M of copolymern=26.9 × 103G/mol, molecular weight distribution PDI=2.05.
[LaL (the O of embodiment 7iPr)]2It is catalyzed L-LA and ε-CL (molar ratio 60:40) copolymerization height random copolymer
L-LA (0.2594g, 1.80mmol) and 6-caprolactone (0.1370g, 1.20mmol) are taken, according to the side of embodiment 3
Method carries out polymerization reaction, obtains L-LA and ε-CL height random copolymer.Product manufactured in the present embodiment is characterized, as a result
It is as follows:
L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-CL- ε-CL chain link=86:14；
Copolymer glass transition temperature: 7.9 DEG C, Average Segment Length: LLA=1.11；LCL=1.11；Obtained solid product is carried out
Gpc analysis measures the M of copolymern=30.7 × 103G/mol, molecular weight distribution PDI=2.01.
[LaL (the O of embodiment 8iPr)]2It is catalyzed L-LA and ε-CL (molar ratio 70:30) copolymerization height random copolymer
L-LA (0.3027g, 2.10mmol) and 6-caprolactone (0.1027g, 0.90mmol) are taken, according to the side of embodiment 3
Method carries out polymerization reaction, obtains L-LA and ε-CL height random copolymer.Product manufactured in the present embodiment is characterized, as a result
It is as follows:
L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-CL- ε-CL chain link=89:11；
Copolymer glass transition temperature: 19.0 DEG C, Average Segment Length: LLA=1.89；LCL=1.02；To obtained solid product into
Row gpc analysis measures the M of copolymern=37.5 × 103G/mol, molecular weight distribution PDI=1.72.
[LaL (the O of embodiment 9iPr)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2274g, 1.58mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1801g, 1.58mmol) is dissolved with 549 μ L toluene.Weigh R=iThe metal Lanthanide complex (6.7mg) of Pr is dissolved in 1000 μ L
Toluene in, take the catalyst solution of 861 μ L (0.0079mmol) to be added in polymerization bottle.It is transferred out of after reacting 3h at 30 DEG C
Glove box, the ethanol solution for being added 95% terminate reaction, are settled with industrial alcohol, filter and multiple washing copolymer, vacuum are dry
Dry 12h obtains L- lactide and 6-caprolactone height random copolymer.
Product is characterized, the conversion ratio that the conversion ratio of L-LA is 88%, ε-CL is 94%；Randomization degree (%):
L-LA- ε-CL chain link: ε-CL- ε-CL chain link=77:23.
Embodiment 10 [LaL (OBn)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2291g, 1.59mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1814g, 1.59mmol) is dissolved with 593 μ L toluene.The metal Lanthanide complex (7.5mg) for weighing R=Bn is dissolved in 1000 μ L's
In toluene, the catalyst solution of 827 μ L (0.0080mmol) is taken to be added in polymerization bottle.It shifts and sells after reaction 3h at 60 DEG C
Casing takes out 60 μ L reaction solutions and carries out original position1HNMR characterization, the ethanol solution for being then added 95% terminates reaction, with industrial wine
Essence sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=80:20.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=17.7 × 103G/mol, point
Son amount distribution PDI=1.81.
Embodiment 11 [LaL (OBn)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2899g, 2.01mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.2296g, 2.01mmol) is dissolved with 953 μ L toluene.The metal Lanthanide complex (9.3mg) for weighing R=Bn is dissolved in 1000 μ L's
In toluene, the catalyst solution of 843 μ L (0.0100mmol) is taken to be added in polymerization bottle.It shifts and sells after reaction 3h at 30 DEG C
Casing takes out 60 μ L reaction solutions and carries out original position1H NMR characterization, the ethanol solution for being then added 95% terminates reaction, with industrial wine
Essence sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=75:25.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=19.4 × 103G/mol, point
Son amount distribution PDI=1.86.
Embodiment 12 [LaL (OEt)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2061g, 1.43mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.1632g, 1.43mmol) is dissolved with 412 μ L toluene.The metal Lanthanide complex (5.9mg) for weighing R=Et is dissolved in 1000 μ L's
In toluene, the catalyst solution of 865 μ L (0.0071mmol) is taken to be added in polymerization bottle.It shifts and sells after reaction 3h at 60 DEG C
Casing takes out 60 μ L reaction solutions and carries out original position1HNMR characterization, the ethanol solution for being then added 95% terminates reaction, with industrial wine
Essence sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=83:17.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=19.9 × 103G/mol, point
Son amount distribution PDI=1.87.
Embodiment 13 [LaL (OEt)]2It is catalyzed L-LA and ε-CL (molar ratio 50:50) copolymerization height random copolymer
Under the protection of glove box High Purity Nitrogen, L-LA (0.2532g, 1.76mmol) and ε-CL are added in Xiang Juhe pressure bottle
(0.2005g, 1.76mmol) is dissolved with 932 μ L toluene.The metal Lanthanide complex (9.9mg) for weighing R=Et is dissolved in 1000 μ L's
In toluene, the catalyst solution of 637 μ L (0.0088mmol) is taken to be added in polymerization bottle.It shifts and sells after reaction 3h at 30 DEG C
Casing takes out 60 μ L reaction solutions and carries out original position1H NMR characterization, the ethanol solution for being then added 95% terminates reaction, with industrial wine
Essence sedimentation, is filtered and multiple washing copolymer, vacuum drying 12h obtain L- lactide and 6-caprolactone height random copolymer.
Find out from In situNMR figure, L-LA and ε-CL conversion is complete；Randomization degree (%): L-LA- ε-CL chain link: ε-
CL- ε-CL chain link=73:27.Gpc analysis is carried out to obtained solid product, measures the M of copolymern=20.7 × 103G/mol, point
Son amount distribution PDI=1.89.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of method for preparing L- lactide and 6-caprolactone random copolymer, which comprises the following steps:
(1) using L- lactide and 6-caprolactone as raw material, matched with the rare earth metal that the bis aryloxy ligand of schiff bases bridging is stable
Conjunction object is catalyst, and 30-60 DEG C occurs ring opening copolymer reaction in organic solvent, obtains L- lactide and 6-caprolactone randomly altogether
Polymers；The stable rare earth metal complex of the bis aryloxy ligand of the schiff bases bridging and L- lactide and 6-caprolactone rub
You are than being 1:120-500:120-500；The stable rare earth metal complex structure of the bis aryloxy ligand of the schiff bases bridging
Shown in formula such as formula (1) and/or formula (2):
Wherein THF is tetrahydrofuran molecule, R 2,6- di-t-butyl p-methylphenyl, tert-butyl, isopropyl, benzyl and ethyl
It is a kind of.
2. according to the method described in claim 1, it is characterized by: the reaction time is 2-7h.
3. according to the method described in claim 1, it is characterized by: the ratio of the catalyst and organic solvent is 2-5mmol:
1mL。
4. according to the method described in claim 1, it is characterized by: the organic solvent is toluene, n-hexane or tetrahydrofuran
One kind.
5. according to the method described in claim 1, it is characterized by: in the L- lactide and 6-caprolactone random copolymer,
The content of L- lactide is 9-90%.
6. according to the method described in claim 1, it is characterized by: in the L- lactide and 6-caprolactone random copolymer,
The content of 6-caprolactone is 10-91%.
7. according to the method described in claim 1, it is characterized by: mole of the catalyst, L- lactide and 6-caprolactone
Than for 1:120-300:120-300.
8. according to the method described in claim 1, it is characterized by also including the step of terminator terminates polymerization reaction is added.
9. according to the method described in claim 8, it is characterized by: the terminator is the hydrochloric acid solution or 95% ethyl alcohol of ethyl alcohol
Solution.
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| CN113549202A (en) * | 2021-08-24 | 2021-10-26 | 濮阳市盛源石油化工（集团）有限公司 | Copolymerized polylactic acid and preparation method thereof |
| CN114853800A (en) * | 2022-06-07 | 2022-08-05 | 山西大学 | Silicon-bridged pyridyl [ N, N ] lithium complex and preparation method and application thereof |
| CN115260217A (en) * | 2022-08-19 | 2022-11-01 | 大连理工大学 | Bridged bisoxazoline rare earth metal catalyst, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113549202A (en) * | 2021-08-24 | 2021-10-26 | 濮阳市盛源石油化工（集团）有限公司 | Copolymerized polylactic acid and preparation method thereof |
| CN114853800A (en) * | 2022-06-07 | 2022-08-05 | 山西大学 | Silicon-bridged pyridyl [ N, N ] lithium complex and preparation method and application thereof |
| CN114853800B (en) * | 2022-06-07 | 2023-12-26 | 山西大学 | Silicon bridged pyridyl [ N, N ] lithium complex, preparation method and application |
| CN115260217A (en) * | 2022-08-19 | 2022-11-01 | 大连理工大学 | Bridged bisoxazoline rare earth metal catalyst, preparation method and application |
| CN115260217B (en) * | 2022-08-19 | 2024-06-07 | 大连理工大学 | Bridged bisoxazoline rare earth metal catalyst, preparation method and application |
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