CN105754078A - Block copolymerization method of PLLA and PEG in supercritical carbon dioxide - Google Patents
Block copolymerization method of PLLA and PEG in supercritical carbon dioxide Download PDFInfo
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- CN105754078A CN105754078A CN201610148327.2A CN201610148327A CN105754078A CN 105754078 A CN105754078 A CN 105754078A CN 201610148327 A CN201610148327 A CN 201610148327A CN 105754078 A CN105754078 A CN 105754078A
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- 229920001432 poly(L-lactide) Polymers 0.000 title claims abstract description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 17
- 238000012661 block copolymerization Methods 0.000 title claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 230000002459 sustained effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 4
- 102400000830 Saposin-B Human genes 0.000 description 4
- 101800001697 Saposin-B Proteins 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a block copolymerization method of PLLA and PEG in supercritical carbon dioxide.The method includes: adding lactide monomer, stannous octoate and polyethylene glycol (PEG) into a reaction kettle for reaction, wherein the mole ratio of the lactide monomer to the stannous octoate to the polyethylene glycol is 60-100:0.2-0.8:10-30; adding 0-10wt% of stabilizer PCL-b-PDMS-b-PCL; feeding CO2 into the reaction kettle until the pressure in the kettle reaches 16-20Mpa, and under 80-100 DEG C, keeping the pressure and temperature in the kettle unchanged to perform continuous reaction for 12-48 hours so as to obtain the block coplymerization product of the PLLA and the PEG.The method has the advantages that the PLLA-b-PEG-b-PLLA block coplymerization product with good comprehensive performance is prepared successfully, the conversion rate of the block coplymerization product can reach above 92%, and the method is short in reaction time, mild in reaction condition and simple in process; organic solvents are not needed, and the method conforms to the development direction of green chemistry; the method is a biological material synthesizing method with development potential and is promising in application prospect.
Description
Technical field
The present invention relates to a kind of PLLA and the method for PEG block copolymerization, particularly to a kind of overcritical dioxy
Change PLLA and the method for PEG block copolymerization in carbon.
Background technology
Linear aliphatic adoption ester has obtained paying close attention to widely and applying as novel degradation material in recent years.
But, traditional preparation method relates to the use of organic solvent, reaction temperature be too high, product property not
Defect and the deficiency such as controlled.CO2The excellent properties such as nontoxic by it, pollution-free, reactionlessness are increasingly becoming
The popular selection of current Polymer Synthesizing process solvent, also became in recent years the research hot topic class of " Green Chemistry "
Topic.Supercritical carbon dioxide, as solvent the most frequently used in supercritical fluid technique, has many advantages: two
Carbonoxide abundance, easy circulation and stress uses, no solvent residue；Carbon dioxide molecule is stable, will not
Cause side reaction.
Having substantial amounts of ester bond in PLLA (PLLA), hydrophily is poor, the most just reduces its bio-compatible
Property；It addition, PLLA degradation cycle is longer, fragility higher toughness is poor, and impact resistance is poor.Poly-second two
Alcohol (PEG) belongs to the preferable degradation material of hydrophily, can improve PLLA by the copolymerization of PEG and PLLA
Hydrophilicity, and PEG can as PLLA polymerization initiator, form block in the way to insert
Copolymer, according to the proportioning of starting monomer, can conveniently design structure and the molecular weight of its copolymer.
Supercritical carbon dioxide can dissolve nonpolar molecule and some polar molecules of most of low-molecular-weight, but
On most industry, widely used polymer but can not be dissolved under the conditions of relatively mild, the most unformed
Fluoropolymer and siloxane polymer can be completely dissolved in supercritical carbon dioxide, therefore, great majority are super
Polymerisation in critical carbon dioxide is heterogeneous, i.e. precipitation polymerization.There are some and lack in precipitation polymerization
Point, as conversion ratio is low, molecular weight of product is less and product form is irregular etc..
Summary of the invention
It is an object of the invention to provide a kind of PLA with good biodegradability properties energy and polyethylene glycol three
The preparation method of block PLLA-b-PEG-b-PLLA copolymer；The method can be at supercritical carbon dioxide ring
Realizing dispersin polymerization in border, the conversion ratio improving raw material is low, and the molecule that synthetic molecular weight is bigger, carries meanwhile
The systematicness of high product molecular conformation.
For reaching above-mentioned purpose, the invention provides PLLA and PEG block in a kind of supercritical carbon dioxide
The method of copolymerization, specifically comprises the following steps that
S1, by lactide monomer (L-LA) drying under reduced pressure 8～12h at 30 DEG C；
S2, by lactide monomer, stannous octoate and polyethylene glycol (PEG) according to 60～100:0.2～0.8:10～30
Mol ratio put in reactor, stir, obtain reactant liquor；Stabilizer is added in described reactant liquor
PCL-b-PDMS-b-PCL, the addition of described stabilizer PCL-b-PDMS-b-PCL is described reactant liquor
0～10wt%；
Wherein, stannous octoate (Sn (Oct)2) it is catalyst；Polyethylene glycol (PEG) is macromole evocating agent；
PCL-b-PDMS-b-PCL is stabilizer, and stabilizer used in the present invention is according to patent " overcritical dioxy
Change carbon dispersin polymerization stabilizer and preparation method thereof good using method (ZL2013101210958) " prepare.
S3, described reactor is vacuumized；
This step is primarily to remove moisture that may be present in demonomerization, catalyst and initiator further.
S4、CO2Purge described reactor and the connecting line with described reactor；
This step is primarily to remove the air in pipeline and in still and moisture further；
S5, in described reactor, it is passed through CO2To still, pressure reaches 16～20MPa, and meanwhile, heating is described
Reactor to temperature in the kettle reaches 80～100 DEG C；Keep pressure in described still, temperature-resistant, sustained response
12～48h；
Reactor is cooled to below supercritical carbon dioxide critical-temperature by S6, use frozen water；
S7, pressure release to CO2Release completely, is taken out product, is obtained PLLA and PEG block copolymer.
Under preferred embodiment, lactide monomer described in step S2 is 80:20 with the mol ratio of described polyethylene glycol；
The 5wt% that addition is described reactant liquor of described stabilizer PCL-b-PDMS-b-PCL.
Under preferred embodiment, step S5 is: be passed through CO in described reactor2To still, pressure reaches 18MPa,
Meanwhile, heat described reactor to temperature in the kettle and reach 100 DEG C；Keep pressure in described still, temperature-resistant,
Sustained response 24h.
Present invention have an advantage that
1, the inventive method has successfully prepared the PLLA-b-PEG-b-PLLA with good combination property
Block copolymerization product, the conversion ratio of lactide monomer can reach more than 92%, and stabilizing agent dosage only needs 3%, instead
Significantly reducing between Ying Shi, reaction condition is gentle, and separating-purifying only need to reduce pressure and get rid of carbon dioxide, technique
Simply；In addition to catalyst and initiator, it is not required to organic solvent, meets the direction of green chemistry；This
Bright method is a kind of biomaterial synthetic method with development potentiality, has broad application prospects.
2, the inventive method successfully achieves dispersin polymerization, has been largely overcoming overcritical titanium dioxide
The shortcoming existing for precipitation polymerization common in carbocyclic ring border, under the effect of stabilizer, it is possible to polymer with
Solvent interface form certain active force, produce steric effect by physical absorption or chemical graft and prevent
The cohesion of particle；The inventive method improves reaction efficiency and yield, and the inventive method can be used for overcritical two
The linear aliphatic adoption ester such as polymerization polylactic acid, polycaprolactone and copolymer thereof in carbonoxide.
The present invention uses supercritical fluid as solvent, and the Biodegradable material of preparation can be made to avoid use to have
Conventional organic solvent, more environmental protection, and later separation are simple, and solvent residual amount is few, overcritical
In fluid, polymerisation is a kind of synthetic process having good prospect.
Accompanying drawing explanation
Fig. 1 is PLLA-b-PEG-b-PLLA synthetic route chart；
Fig. 2 is PLLA-b-PEG-b-PLLA block copolymerization reaction experiment installation drawing in supercritical carbon dioxide；
Fig. 3 is the 1H-NMR spectrogram of PLLA-b-PEG-b-PLLA block copolymerization product；
Fig. 4 is the DSC collection of illustrative plates of PLLA-b-PEG-b-PLLA block copolymerization product.
Detailed description of the invention
PLLA in supercritical carbon dioxide involved by following embodiment and the road of PEG block copolyreaction
Line, as shown in Figure 1；Reaction unit involved by embodiment is: volume 50ml with sapphire visual window,
Equipped with electromagnetic stirring system and numerical control electric heating system autoclave (the highest operation pressure 30MPa,
Maximum allowable operating temperature (M.A.O.T.) 150 DEG C), reactor the most first uses dichloromethane clean and use hot blast to make it
Fully it is dried.
Reaction process chart as shown in Figure 2: wherein, 1 is CO2Gas cylinder, 2 is cylinder pressure gauge, 3
Being gas cylinder valve, 4 is cooler, and 5 is plunger displacement pump, and 6 is Pressure gauge, and 7 is reactor inlet valve, and 8 is pressure
Power table, 9 is sapphire visual window, and 10 is magnetic stirring apparatus, and 11 is electric heating chuck, and 12 is air bleeding valve,
13 is heating tape, and 14 is collection device, and 15 is bleeder valve, and 16 is flowmeter.
Embodiment of the present invention PROCESS OVERVIEW is:
In advance monomer drying under reduced pressure at 30 DEG C is overnight removed water；Dichloromethane is used to clean reactor before experiment
And use hot blast to make it the driest；Monomer (L-LA), catalyst (Sn (Oct) 2) and big molecule are drawn
Send out agent (PEG) and put in reactor according to the molar ratio of 60:0.2:10～100:0.8:30, add self-control
Stabilizing agent dosage be 0～10wt%；Use vavuum pump reactor is vacuumized demonomerization, catalyst and
Moisture that may be present in initiator；Use CO2Purging reactor and pipeline, remove in pipeline and in still
Air and moisture；Close outlet valve, use plunger displacement pump to be passed through CO in reactor2, simultaneously to reactor
Heating, adjusts pressure and temperature to setting value as required；Keep pressure and temperature constant, continue 12～48h
Reaction time, then use frozen water reactor is cooled to below critical-temperature；Open outlet valve, slowly
Pressure release, treats CO2Release completely, opens reactor, takes out product.
It is embodied as example below by several the present invention will be further described.
Embodiment 1
The block copolymerization dispersin polymerization of L-lactide (L-LA) and polyethylene glycol (PEG) is at 50ml stainless steel
Reactor is carried out, as shown in Figure 2.In advance monomer drying under reduced pressure at 30 DEG C is overnight removed water；Before experiment
Dichloromethane is used to clean reactor and use hot blast to make it the driest；Add monomer L-LA1.6g, PEG
0.4g, 0.1g (5%) stabilizer, 45mg stannous octoate and polytetrafluoroethylene (PTFE) rotor, sealed reactor.
The most logical CO2Heat after 5min, open plunger displacement pump simultaneously and system is pressurizeed, reach experimental temperature
After (80 DEG C) and reaction pressure (18MPa), start agitator；Reaction 24h, stops heating and stirring, reaction
Still naturally stirs and is cooled to room temperature, slowly exits.Opening reactor, collect white powder product, number is all
Molecular weight (Mn) is 12800, and molecular weight distribution (PDI) is 1.18, productivity 78%.
Embodiment 2
Concrete operations with example 2, add monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer,
45mg stannous octoate, experimental temperature (90 DEG C), reaction pressure (18MPa), reaction time 24h, product is
White powder, number-average molecular weight (Mn) is 15255, and molecular weight distribution (PDI) is 1.13.Productivity 88%.
Embodiment 3
Concrete operations with example 2, add monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer,
45mg stannous octoate, experimental temperature (100 DEG C), reaction pressure (18MPa), reaction time 24h, product is
White powder, number-average molecular weight (Mn) is 15380, and molecular weight distribution (PDI) is 1.15, productivity 90%.
Fig. 3 is monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer, 45mg stannous octoate,
Experimental temperature (90 DEG C), reaction pressure (18MPa), reaction time 24h, PLLA-b-PEG-b-PLLA are embedding
The 1H-NMR spectrogram of section copolymerization product.Being positioned at peak the most sharp-pointed at 1.5ppm is-CH3 weight in PLLA
The characteristic peak of multiple unit, being positioned at the peak at 5.2ppm is the peak corresponding to-CH-, and both combines provable
Product has the existence of PLLA；Be positioned at 3.6ppm unimodal for the i.e. ethylene glycol of O-CH2-CH2-O-repeat
The characteristic peak of structure, this peak is the conclusive evidence that there is PEG in construction unit；And be positioned at 4.3ppm
The structure corresponding to faint peak be-COOCH2-C-, the presence or absence at this peak decides whether copolymerization is sent out
Raw, at this, peak value is the peak value of PEG Yu PLLA building block junction, and at this, peak value exists explanation product
For the block copolymer of PEG and PLLA rather than the blend of PLLA Yu PEG, Fig. 3 can be concluded that reality
Subject copolymers has been synthesized in testing.
Fig. 4 is the DSC collection of illustrative plates of PLLA-b-PEG-b-PLLA block copolymerization product.In comparison diagram
The DSC plot of PLLA-b-PEG-b-PLLA and PLLA can significantly see the difference of the two thermophysical property
Not.Copolymer also exists two obvious peaks, lays respectively at 125 DEG C and about 150 DEG C, its generation respectively
The table melting peak of PEG and PLLA, and the melting peak of simple PLLA is about about 160 DEG C, PLLA
In structure, the introducing of PEG chain segment destroys the regularity of its segment to a certain extent so that its crystal property
Declining, heat endurance also occurs in that and significantly weakens therewith.The melt temperature of PLLA segment occurs slight
Declining, its reason is likely due to the length of single PLLA segment and has declined caused thermally-stabilised
Property occurs in that decline.In DSC curve, two kinds of polymer all do not have corresponding to obvious glass transition temperature
Peak occurs, thus the crystal property of two kinds of products of explanation is preferable, and the isotactic characteristic of product is good.
In the inventive method, the conversion ratio of product is affected notable by temperature, along with the raising of temperature, product
The trend that conversion ratio is significantly improved, molecular weight of product is also with raising simultaneously, and especially temperature is by 80 DEG C
It is increased to when 90 DEG C the most obvious.The polymerization of 1H-NMR analytical proof has obtained three blocks that structure is clear and definite
PLLA-b-PEG-b-PLLA copolymer.The thermal physical characteristic of the product after DSC and TGA display modification by copolymerization
Matter there occurs significantly change, and PLLA-b-PEG-b-PLLA all occurs in that significantly relative to PLLA fusing point
Decline.Granularmetric analysis shows along with the increase of the content of PEG in copolymer, the average grain diameter of product and particle diameter
Distribution all occurs in that obvious increase tendency, and this is that product is instead mainly due to the reduction of melting temperature
There occurs softening at a temperature of Ying and adhere to.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope of present disclosure, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (3)
1. PLLA and the method for PEG block copolymerization in a supercritical carbon dioxide, it is characterised in that tool
Body step is as follows:
S1, by lactide monomer drying under reduced pressure 8～12h at 30 DEG C；
S2, by lactide monomer, stannous octoate and polyethylene glycol according to 60～100:0.2～0.8:10～30 mole
Than putting in reactor, stir, obtain reactant liquor；Stabilizer is added in described reactant liquor
PCL-b-PDMS-b-PCL, the addition of described stabilizer PCL-b-PDMS-b-PCL is described reactant liquor
0～10wt%；
S3, described reactor is vacuumized；
S4、CO2Purge described reactor and the connecting line with described reactor；
S5, in described reactor, it is passed through CO2To still, pressure reaches 16～20MPa, and meanwhile, heating is described
Reactor to temperature in the kettle reaches 80～100 DEG C；Keep pressure in described still, temperature-resistant, sustained response
12～48h；
Reactor is cooled to below supercritical carbon dioxide critical-temperature by S6, use frozen water；
S7, pressure release to CO2Release completely, is taken out product, is obtained PLLA and PEG block copolymer.
PLLA and the method for PEG block copolymerization in supercritical carbon dioxide the most according to claim 1,
It is characterized in that, lactide monomer described in step S2 is 80:20 with the mol ratio of described polyethylene glycol；Institute
State the 5wt% that addition is described reactant liquor of stabilizer PCL-b-PDMS-b-PCL.
PLLA and the method for PEG block copolymerization in supercritical carbon dioxide the most according to claim 1,
It is characterized in that, step S5 is: be passed through CO in described reactor2To still, pressure reaches 18MPa, with
Time, heat described reactor to temperature in the kettle and reach 100 DEG C；Keep pressure in described still, temperature-resistant, hold
Continuous reaction 24h.
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| CN201610148327.2A CN105754078B (en) | 2016-03-16 | 2016-03-16 | PLLA and the method for PEG block copolymerization in a kind of supercritical carbon dioxide |
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| CN201610148327.2A CN105754078B (en) | 2016-03-16 | 2016-03-16 | PLLA and the method for PEG block copolymerization in a kind of supercritical carbon dioxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432741A (en) * | 2016-09-09 | 2017-02-22 | 大连大学 | Preparation method of folic acid grafted PLLA-PEG-PLLA copolymer |
| CN107163237A (en) * | 2017-05-27 | 2017-09-15 | 大连大学 | The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers |
| CN109453114A (en) * | 2018-11-21 | 2019-03-12 | 温州医科大学 | A kind of copolymeric micelles drug-loading nanoparticles and its application |
| CN114807252A (en) * | 2022-04-25 | 2022-07-29 | 大连大学 | Method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide |
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| CN106432741A (en) * | 2016-09-09 | 2017-02-22 | 大连大学 | Preparation method of folic acid grafted PLLA-PEG-PLLA copolymer |
| CN106432741B (en) * | 2016-09-09 | 2019-09-13 | 大连大学 | A kind of preparation method based on folic acid grafting PLLA-PEG-PLLA copolymer |
| CN107163237A (en) * | 2017-05-27 | 2017-09-15 | 大连大学 | The method that hydrogen chloride/diethyl ether solution catalysis prepares PCL PDMS PCL stabilizers |
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| CN114807252A (en) * | 2022-04-25 | 2022-07-29 | 大连大学 | Method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide |
| CN114807252B (en) * | 2022-04-25 | 2024-04-12 | 大连大学 | Synthesis method of four-arm star polylactic acid in supercritical carbon dioxide |
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