CN107880254A - A kind of poly (l-lactic acid) cyclodextrin copolymers material and preparation method thereof - Google Patents
A kind of poly (l-lactic acid) cyclodextrin copolymers material and preparation method thereof Download PDFInfo
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- CN107880254A CN107880254A CN201711441202.XA CN201711441202A CN107880254A CN 107880254 A CN107880254 A CN 107880254A CN 201711441202 A CN201711441202 A CN 201711441202A CN 107880254 A CN107880254 A CN 107880254A
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- lactic acid
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The invention belongs to technical field of polymer materials.The invention discloses the preparation method of the copolymer material of poly- L lactic acid cyclodextrin.Raw material L lactic acid and cyclodextrin are added in reactor, the mass ratio of cyclodextrin and L lactic acid is 0.5/99.5~35/65,150~180 DEG C of 0~4h of constant temperature under normal pressure, add the pink salt and sulfoacid compound catalyst for accounting for reactant gross mass 0.01~6.0%, 160~200 DEG C are warming up to, 2~12h of isothermal reaction under 0~30mm mercurypressures.The product of gained is separated using solution deposit, after vacuum drying, the poly- L lactic acid cyclodextrin copolymers purified.The relative molecular mass of poly- L lactic acid cyclodextrin copolymers is 6000~150000, and wherein cyclodextrin content is 0.1~35.0%.
Description
Technical field：
The invention belongs to technical field of polymer materials, and in particular to the copolymer material of poly (l-lactic acid) and cyclodextrin and its
Preparation method and application.
Background technology：
A kind of biodegradable polyester of the PLA (PLA) as synthesis, it is gradual in increasing environmental pollution, petroleum resources
Exhaust and situation that people's environmental consciousness increasingly strengthens under, be certainly most potential environment-friendly materials.PLA is by L-
Lactic acid is derived, and is mainly synthesized by sugared fermenting raw materials, due to its biocompatibility and biodegradable, in medical field and
Packaging material field is widely used.But PLA has hydrophobicity, the adhesiveness of its cell is poor, as tissue
It may cause inflammatory reaction after engineering material implantation organism.In addition, linear polylactic acid is crystallization rate is slow, crystallinity is low, crisp
The aspects such as property height have the limitation of its own, all significantly limit its application.Therefore, can in order to improve the performance of PLA
Introduce new polymer segment and carry out copolymerization and prepare copolymer.With hydrophilic monomer or polymer such as monose, polyethylene glycol, shell
Glycan and polysaccharide etc. are copolymerized, and the research of modification by copolymerization PLA increasingly causes concern.
Cyclodextrin (CD) is to act on the grapes such as starch, glycogen, malt oligosaccharide by cyclodextrin glucose residue transferase
Glycopolymers and formed, the cyclic oligomer being formed by connecting by 6~12 D- glucopyranosyls with α-Isosorbide-5-Nitrae-glucoside bond
Sugar.More than research relatively and what application was wider has three kinds, i.e. α, β, γ-CD.Cyclodextrin inner is hydrophobic, the property of external hydrophilic
Matter makes its existing water solubility, can form host-guest molecule or super molecular complex by hydrophobic component bag in its cavity again.
Cyclodextrin has unique hollow structure, and many suitable compounds of size, particularly aromatic compound can dredge into it
Water cavity forms the host-gust inclusion complexes of non-covalent bond bonding.Beta-schardinger dextrin is a kind of hydrophilic oligosaccharide, and molecular formula is
C42H70O35, be combined into by 7 glucose units with Isosorbide-5-Nitrae-glycosidic bond, wherein C3, C5 position have in cavity and cover with sugar
Oxygen atom, makes cavity inside turn into hydrophobic space, and cavity edge contains hydroxyl, makes have water imbibition outside cavity.It is special using this
Different structure, beta-schardinger dextrin can be combined into Host-guest inclusion complex with many inorganic, organic molecules, and can change by the chemistry of inclusion compound
And physical property, have protection, stably, the characteristic of solubilized guest molecule and selective oriented molecule.It is mainly used in medicine at present
The fields such as thing sustained release, also valency is applied with higher in organic synthesis, pharmaceutical engineering, environmental protection and Medical Adsorbents etc.
Value.
PLA cyclodextrin copolymers material is mainly what is be prepared by the method for melt polycondensation, uses cyclo-dextrin-modified
Copolymer of poly lactic acid material, not only remain the degradability of PLA, can also improve the various performances of PLA.
Youngjae Byun etc. research and analyse out beta-schardinger dextrin using master-objective complex compound that PLA and beta-schardinger dextrin are prepared comprising method
The thermal expansion stability of the lactic acid composite material of copolymerization has obvious improvement (International Journal of
Biological Macromolecules, 2015,81：591-598.).Silica is cladded with by Hossein Ansari etc.
Magnetic ferroferric oxide is chemically grafted to beta-schardinger dextrin (β-CD@Fe3O4), and it is compound with solvent casting method to prepare polylactic acid nano
Thing.Confirm β-CD@Fe3O4The heat and combustibility (Polymer-Plastics Technology and of PLA can be improved
Engineering, 2017,56 (12)：1366-1373.).G.Vermet etc. improves PLA antibacterial using cyclodextrin
Be implanted into net bank property and antibacterial effect (Acta Biomaterialia, 2017,53：222-232.).Zhu Jiujin etc. is used
N- acylation reactions, maleic anhydride modified PLA (MPLA) macromolecular chain is arrived by 6- amidos beta-schardinger dextrin (β-CD-6-E) is immobilized
On, the hydrophily and cell compatibility of obtained new cyclo-dextrin-modified polylactic acid radical biological material (PLA- β-CD) have substantially
Improve (functional material, 2011,1 (42)：17-20.).
From it is found that poly-lactic acid in high molecular weight can degrade in human body and behind this kind of material introducing biologic applications field,
Significant progress has been obtained to its in-depth study and application.PLA is commonly used for carrier and surgical repair of medicine transport etc.
Bio-medical material, but its hydrophobicity and limit its application with the shortcomings of cell compatibility difference.And cyclodextrin is as starch
In the presence of enzyme a kind of caused hydrophily, there is the natural material of special molecular structure, can after modified and producing high-molecular
Applied to fields such as medicament slow releases, the compatibility of poly-lactic acid material can be improved, the combination property of material is improved, expand it in medicine
The application in the field such as carrier and medical material.
The content of the invention：
The purpose of the present invention is the hydrophobicity for poly (l-lactic acid), common therewith using a kind of efficient, green raw material
It is poly- to be modified, so as to improve the cellular affinity of poly (l-lactic acid), and then provide a kind of convenience, the poly (l-lactic acid) cyclodextrin copolymerization of environmental protection
The preparation method of thing material, the hydrophobicity and biocompatibility of the copolymer of gained make moderate progress.
Technical scheme is as follows used by realizing the object of the invention：
The preparation method of poly (l-lactic acid) cyclodextrin copolymers：The present invention is with Pfansteihl (LLA), poly (l-lactic acid) and cyclodextrin
(CD) it is raw material, poly (l-lactic acid) cyclodextrin copolymers is prepared using the method for direct melt polycondensation.
The step of preparation process of described poly (l-lactic acid) cyclodextrin copolymers includes：Raw material Pfansteihl and cyclodextrin are added
In reactor, stirred under normal pressure, 0~4h of isothermal reaction, then adds catalyst after being warming up to 150~180 DEG C, is warming up to 160
It is decompressed to after~200 DEG C under 0~30mm mercurypressures, then 2~12h of isothermal reaction.After the product of gained is dissolved with chloroform,
Precipitated and separated with precipitating reagent again, the sediment of gained is dried in vacuo 10~15h at 50 DEG C, the poly (l-lactic acid) ring paste purified
Smart copolymer.The copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, is copolymerized for the poly-L-lactic acid cyclodextrin of purifying
Thing.The relative molecular mass of the copolymer of gained is 6000~150000, and wherein cyclodextrin content is 0.1~35.0%, poly- L-
Lactic acid segment content is 65.0~99.9%.
Further, described copolymer can also use the following steps to prepare：After poly (l-lactic acid) is purified, in reactor
In be heated to after melting completely, add cyclodextrin and catalyst, be decompressed under 0~30mm mercurypressures, in 160~200 DEG C of perseverances
2~12h of temperature reaction.After the product of gained is dissolved with chloroform, then with precipitating reagent Precipitation, the sediment isolated is 50
10~15h, the poly (l-lactic acid) cyclodextrin copolymers purified are dried in vacuo at DEG C.The copolymer of gained uses nuclear magnetic resoance spectrum
Method carries out structural characterization, for the poly (l-lactic acid) cyclodextrin copolymers of purifying.
Further, described copolymer can also use the following steps to prepare：Using Pfansteihl as raw material, first pre-polymerization removes
Water in lactic acid, then temperature is by 150~200 DEG C, and under step-by-step decompression to 10~50mm mercurypressures, polycondensation reaction obtains poly- L-
Lactic acid, cyclodextrin and catalyst are added, be decompressed under 0~30mm mercurypressures, in 160~200 DEG C of 2~12h of isothermal reaction.
After the product of gained is dissolved with chloroform, then with precipitating reagent Precipitation, the sediment isolated is dried in vacuo at 50 DEG C
10~15h, the poly (l-lactic acid) cyclodextrin copolymers purified.The copolymer of gained carries out structure table using nuclear magnetic resonance spectrometry
Sign, for the poly (l-lactic acid) cyclodextrin copolymers of purifying.
Further, described copolymer in the preparation, the mass ratio of starting cyclodextrin and Pfansteihl for 0.5/99.5~
35..0/65.0。
Further, the relative molecular mass of described poly (l-lactic acid) is 5000~80000.Cyclodextrin and and poly (l-lactic acid)
Mass ratio be 0.5/99.5~35..0/65.0.
Further, in the preparation, cyclodextrin contains 6~12 D- glucopyranose units to described copolymer, be α-
Cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin and big ring cyclodextrin.
Further, the method for purification of described copolymer can also be made by the steps：With apparatus,Soxhlet's, use
Toluene extracts 224h, removes poly (l-lactic acid) homopolymer.
Further, described catalyst is the mixture of pink salt, one kind in sulfoacid compound or its arbitrary proportion, is urged
Agent dosage is the 0.01~6.0% of reactant gross mass.Tin compound is SnCl2、SnCl4, stannous iso caprylate and stannous octoate
In any one or two or more arbitrary proportions mixture.Sulfoacid compound be benzene sulfonic acid, p-methyl benzenesulfonic acid, naphthalene sulfonic acids,
It is any one in naphthalenedisulfonic acid and benzene sulfonic acid containing methyl, methylol, ethyl, propyl group or isopropyl, naphthalene sulfonic acids and naphthalenedisulfonic acid
The mixture of kind or two or more arbitrary proportions.
Further, described copolymer purification when, precipitating reagent can be methanol, ethanol, one kind in ether or its
The mixture of arbitrary proportion.Depositing technology can be completed with a step, can also in different precipitating reagents in two steps or multistep complete.It is poly-
Sedimentation time of the Pfansteihl cyclodextrin copolymers in precipitating reagent is 1~24 hour.
The present invention prepares poly (l-lactic acid) and cyclodextrin copolymers using the method for direct melt polycondensation, and technique is simple, cost
It is relatively low, cyclodextrin and lactic raw material abundance.Poly (l-lactic acid) and the cyclodextrin copolymers of the present invention have compatibility preferably, into
The features such as this is low, environmentally degradable, can be used as sustained-release drug carrier.
Embodiment：
Technical scheme is described further with reference to specific embodiment., can according to following embodiments
To more fully understand the present invention.However, specific material proportion, process conditions and its result described by embodiment are only used for
The bright present invention, embodiment are not defined to the scope of the present invention.
Embodiment 1：
The beta-schardinger dextrin and Pfansteihl that mol ratio is 1: 350 are weighed, adds in reactor, 150 DEG C, under normal pressure is warming up under stirring
1h is stirred, is well mixed L lactic acid and beta-schardinger dextrin.Then -0.8Mpa is decompressed to, 4h is reacted, fully removes in reaction system
Water.The catalyst stannous chloride of total reactant quality 0.5% is put into, rise temperature is decompressed to 10mm mercury column pressures to 170 DEG C
Under power, 6h is reacted.Obtained product is dissolved with chloroform, and methanol solution separates out, and is precipitated.Filter precipitation and separation.Obtain
Be deposited at 50 DEG C and be dried in vacuo 10h, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly- of purifying
Pfansteihl cyclodextrin copolymers, it is 55000 that it, which counts equal relative molecular mass,.
Embodiment 2：
The beta-schardinger dextrin and Pfansteihl that mol ratio is 1: 700 are weighed, adds in reactor, 150 DEG C, under normal pressure is warming up under stirring
1h is stirred, is well mixed L lactic acid and beta-schardinger dextrin.Then -0.8Mpa is decompressed to, 4h is reacted, fully removes in reaction system
Water.The catalyst stannous chloride of total reactant quality 0.5% is put into, rise temperature is decompressed to 0mm mercury column pressures to 170 DEG C
Under power, 6h is reacted.Obtained product is dissolved with chloroform, is separated out and precipitated with methanol solution.Being deposited at 50 DEG C for gained is true
Sky dries 10h, and the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, is copolymerized for the poly (l-lactic acid) cyclodextrin of purifying
Thing, it is 165000 that it, which counts equal relative molecular mass,.
Embodiment 3：
The beta-schardinger dextrin and Pfansteihl that mol ratio is 1: 1400 are weighed, adds in reactor, 150 DEG C is warming up under stirring, normal pressure
Lower stirring 1h, is well mixed L lactic acid and beta-schardinger dextrin.Then -0.8Mpa is decompressed to, 4h is reacted, fully removes reaction system
In water.The stannous chloride and stannous iso caprylate mixture catalyzer (mol ratio 1: 1) of total reactant quality 0.5% are put into,
Temperature is raised to 170 DEG C, and is decompressed under 5mm mercurypressures, reacts 6h.Obtained product is dissolved with chloroform, excessive
Methanol separates out precipitation.Being deposited at 50 DEG C for obtaining is dried in vacuo 10h, and the copolymer of gained is tied using nuclear magnetic resonance spectrometry
Structure characterizes, and for the poly (l-lactic acid) cyclodextrin copolymers of purifying, it is 165000 that it, which counts equal relative molecular mass,.
Embodiment 4：
The beta-schardinger dextrin and Pfansteihl that mol ratio is 1: 2100 are weighed, adds in reactor, 150 DEG C is warming up under stirring, normal pressure
Lower stirring 1h, is well mixed L lactic acid and beta-schardinger dextrin.Then -0.8Mpa is decompressed to, 4h is reacted, fully removes reaction system
In water.The catalyst stannous chloride and naphthalene sulfonic acids catalyst of total reactant quality 0.5% are put into, raises temperature to 170 DEG C, and
It is decompressed under 0mm mercurypressures, reacts 6h.Obtained product is dissolved with chloroform, and excessive methanol separates out precipitation.Obtain
It is deposited at 50 DEG C and is dried in vacuo 10h, the copolymer of gained uses nuclear magnetic resonance spectrometry to carry out structural characterization as poly (l-lactic acid) ring
Dextrin copolymer, it is 165000 that it, which counts equal relative molecular mass,.
Embodiment 5：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 1 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
170 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 10mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) ring of purifying
Dextrin copolymer, it is 6000 that it, which counts equal relative molecular mass,.
Embodiment 6：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 5 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
170 DEG C, beta-schardinger dextrin and catalyst stannous iso caprylate are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 15mm
Under mercurypressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.Obtained precipitation
10h is dried in vacuo at 50 DEG C, the copolymer of gained uses nuclear magnetic resonance spectrometry to carry out structural characterization as poly (l-lactic acid) cyclodextrin
Copolymer, it is 15000 that it, which counts equal relative molecular mass,.
Embodiment 7：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 10 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 170 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 2mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, and it counts equal relative molecular mass
For 35000.
Embodiment 8：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 15 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 170 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 3mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) ring of purifying
Dextrin copolymer, it is 11000 that it, which counts equal relative molecular mass,.
Embodiment 9：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 1 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 10mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, and it counts equal relative molecular mass
For 8000.
Embodiment 10：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 5 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
180 DEG C, beta-schardinger dextrin, stannous chloride and Catalyzed by p-Toluenesulfonic Acid agent are added after poly (l-lactic acid) thawing, opens agitator, and subtract
It is depressed under 4mm mercurypressures, reacts 6h.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.Obtain
Be deposited at 50 DEG C and be dried in vacuo 10h, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly- of purifying
Pfansteihl cyclodextrin copolymers, it is 12000 that it, which counts equal relative molecular mass,.
Embodiment 11：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 10 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 0mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) ring of purifying
Dextrin copolymer, it is 16000 that it, which counts equal relative molecular mass,.
Embodiment 12
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 15 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 6mm mercury
Under column pressure, 6h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) ring of purifying
Dextrin copolymer, it is 13000 that it, which counts equal relative molecular mass,.
Embodiment 13：
The beta-schardinger dextrin and Pfansteihl that mol ratio is 1: 700 are weighed, adds in reactor, 150 DEG C, under normal pressure is warming up under stirring
1h is stirred, is well mixed L lactic acid and beta-schardinger dextrin.Then -0.8Mpa is decompressed to, 4h is reacted, fully removes in reaction system
Water.The catalyst stannous chloride of total reactant quality 6% is put into, rise temperature is decompressed to 0mm mercurypressures to 170 DEG C
Under, react 6h.Obtained product is dissolved with chloroform, and methanol solution separates out precipitation.The obtained vacuum at 50 DEG C that is deposited in is done
Dry 10h, the copolymer of gained carry out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) cyclodextrin copolymers of purifying,
It is 110000 that it, which counts equal relative molecular mass,.
Embodiment 14：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 10 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 1mm mercury
Under column pressure, 9h is reacted.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.What is obtained is deposited in
10h is dried in vacuo at 50 DEG C, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for the poly (l-lactic acid) ring of purifying
Dextrin copolymer, it is 18000 that it, which counts equal relative molecular mass,.
Embodiment 15：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 1 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and in 1mm mercurypressures
Lower reaction 9h.Obtained product is dissolved with chloroform, and excessive methanol solution separates out precipitation.Being deposited at 50 DEG C for obtaining is true
Sky dries 10h, and the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, is copolymerized for the poly (l-lactic acid) cyclodextrin of purifying
Thing, it is 12000 that it, which counts equal relative molecular mass,.
Embodiment 16
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 15 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is heated up
To 180 DEG C, beta-schardinger dextrin and catalyst stannous chloride are added after poly (l-lactic acid) thawing, opens agitator, and be decompressed to 1mm mercury
Under column pressure, 7h is reacted.Obtained product is dissolved with chloroform, and methanol separates out with alcohol mixed solution (volume ratio 1: 1)
Precipitation.Being deposited at 50 DEG C for obtaining is dried in vacuo 10h, and the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry,
For the poly (l-lactic acid) cyclodextrin copolymers of purifying, it is 13000 that it, which counts equal relative molecular mass,.
Embodiment 18：
The beta-schardinger dextrin and poly (l-lactic acid) that mol ratio is 1: 5 are weighed, first poly (l-lactic acid) is fitted into three neck round bottom, is warming up to
170 DEG C, gamma-cyclodextrin, stannous chloride and Catalyzed by p-Toluenesulfonic Acid agent are added after poly (l-lactic acid) thawing, opens agitator, and
It is decompressed under 1mm mercurypressures, reacts 6h.Obtained product is dissolved with chloroform, and excessive ethanol solution separates out precipitation.
To be deposited at 50 DEG C and be dried in vacuo 10h, the copolymer of gained carries out structural characterization using nuclear magnetic resonance spectrometry, for purifying
Poly (l-lactic acid) cyclodextrin copolymers, it is 15000 that it, which counts equal relative molecular mass,.
Claims (9)
- A kind of 1. copolymer of PLA and cyclodextrin, it is characterised in that：The relative molecular mass of described copolymer is 6000 ~150000, the mass content of its cyclodextrin segment is 0.1~35.0%, the mass content of poly (l-lactic acid) segment for 65.0~ 99.9%.
- 2. cyclodextrin and copolymer of poly lactic acid described in claim 1, it is characterised in that：Realized with the following steps：By raw material L- Lactic acid and cyclodextrin are added in reactor, are stirred under normal pressure, 0~4h of constant temperature after being warming up to 150~180 DEG C, then add catalysis Agent, it is warming up to 160~200 DEG C, is decompressed to 0~30mm mercurypressures, then 2~12h of isothermal reaction.Three chloromethanes of the product of gained After alkane dissolving, then with precipitating reagent Precipitation, the sediment isolated is dried in vacuo 10~15h at 50 DEG C, is purified Poly (l-lactic acid) cyclodextrin copolymers.
- 3. cyclodextrin and copolymer of poly lactic acid described in claim 1, it is characterised in that：Described poly (l-lactic acid) cyclodextrin copolymerization Product can also use following manner to prepare：Poly (l-lactic acid) is heated to after melting completely, adds cyclodextrin and catalyst, decompression To 0~30mm mercurypressures, in 160~200 DEG C of 2~12h of isothermal reaction.After the product of gained is dissolved with chloroform, then With precipitating reagent Precipitation, the sediment isolated is dried in vacuo 10~15h at 50 DEG C, the poly (l-lactic acid) ring paste purified Smart copolymer.
- 4. the copolymer of the PLA cyclodextrin described in claim 1, it is characterised in that：Described cyclodextrin contains 6~12 D- pyrans grape sugar units, it is alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin and big ring cyclodextrin.
- 5. the copolymer of the poly (l-lactic acid) cyclodextrin described in claim 2 and 3, it is characterised in that：The matter of cyclodextrin and Pfansteihl It is 0.5/99.5~35..0/65.0 to measure ratio, and the mass ratio of cyclodextrin and poly (l-lactic acid) is 0.5/99.5~35..0/65.0.
- 6. the copolymer of the poly (l-lactic acid) cyclodextrin described in claim 3, it is characterised in that：Relative point of described poly (l-lactic acid) Protonatomic mass is 5000~80000.
- 7. the copolymer of the poly (l-lactic acid) cyclodextrin described in claim 2 and 3, it is characterised in that：Described catalyst be pink salt, The mixture of one kind or its arbitrary proportion in sulfoacid compound, catalyst amount are the 0.01~6.0% of reactant gross mass. Tin compound is SnCl2、SnCl4, any one or two or more arbitrary proportions in stannous iso caprylate and stannous octoate mixing Thing.Sulfoacid compound is benzene sulfonic acid, p-methyl benzenesulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid and containing methyl, methylol, ethyl, propyl group or different The mixture of any one or two or more arbitrary proportions in the benzene sulfonic acid of propyl group, naphthalene sulfonic acids and naphthalenedisulfonic acid.
- 8. the copolymer of the poly (l-lactic acid) cyclodextrin described in claim 2 and 3, it is characterised in that：Described copolymer is purifying When, precipitating reagent can be the mixture of methanol, ethanol, one kind in ether or its arbitrary proportion.Depositing technology can be complete with a step Into, can also in different precipitating reagents in two steps or multistep complete.Precipitation of the poly (l-lactic acid) cyclodextrin copolymers in precipitating reagent Time is 1~24 hour.
- 9. the copolymer of the poly (l-lactic acid) cyclodextrin described in claim 2 and 3, it is characterised in that：Described copolymer can also lead to Following method is crossed further to purify：With apparatus,Soxhlet's, 1~24h is extracted with toluene, removes poly (l-lactic acid) homopolymer.
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