CN105754078B - PLLA and the method for PEG block copolymerization in a kind of supercritical carbon dioxide - Google Patents
PLLA and the method for PEG block copolymerization in a kind of supercritical carbon dioxide Download PDFInfo
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- CN105754078B CN105754078B CN201610148327.2A CN201610148327A CN105754078B CN 105754078 B CN105754078 B CN 105754078B CN 201610148327 A CN201610148327 A CN 201610148327A CN 105754078 B CN105754078 B CN 105754078B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229920001432 poly(L-lactide) Polymers 0.000 title claims abstract description 42
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 title claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 238000012661 block copolymerization Methods 0.000 title claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001400 block copolymer Polymers 0.000 claims abstract description 5
- 230000004044 response Effects 0.000 claims abstract description 4
- 230000002459 sustained effect Effects 0.000 claims abstract description 4
- 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 4
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 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
- 102400000830 Saposin-B Human genes 0.000 description 3
- 101800001697 Saposin-B Proteins 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 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
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- 125000005473 octanoic acid group 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
- -1 silicon Oxygen alkane Chemical class 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion 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
- 238000004519 manufacturing process Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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 PLLA in a kind of supercritical carbon dioxide and the method for PEG block copolymerization, specific steps include：By lactide monomer, stannous octoate and polyethylene glycol according to 60~100:0.2~0.8:10~30 mol ratio input reaction；Add 0~10wt% stabilizer PCL b PDMS b PCL；CO is passed through into the reactor2Pressure reaches 16~20Mpa in kettle, at 80~100 DEG C, keeps pressure, temperature-resistant, 12~48h of sustained response in the kettle；Obtain PLLA and PEG block copolymer.The inventive method has successfully prepared the PLLA b PEG b PLLA block copolymerization products with good combination property, and the conversion ratio of lactide monomer can reach more than 92%, and the reaction time is short, and reaction condition is gentle, and technique is simple；Organic solvent is not required to, meets the direction of green chemistry；The inventive method is a kind of biomaterial synthetic method with development potentiality, is had broad application prospects.
Description
Technical field
The present invention relates to a kind of PLLA and the method for PEG block copolymerization, in more particularly to a kind of supercritical carbon dioxide
PLLA and the method for PEG block copolymerization.
Background technology
Linear aliphatic adoption ester has obtained extensive concern and application in recent years as new degradation material.But,
Defect and the deficiency such as the use, the reaction temperature that are related to organic solvent in traditional preparation method are too high, product property is uncontrollable.
CO2The popular choosing of current Polymer Synthesizing process solvent is increasingly becoming by excellent properties such as its nontoxic, pollution-free, reactionlessnesses
Select, the research hot topic problem also as " Green Chemistry " in recent years.Supercritical carbon dioxide as in supercritical fluid technique most
Conventional solvent, has many advantages：Carbon dioxide abundance, easy circulation and stress is used, no solvent residue；Carbon dioxide
Molecule is stable, will not cause side reaction.
There is substantial amounts of ester bond in PLLA (PLLA), hydrophily is poor, also just reduce its biocompatibility；Separately
Outside, PLLA degradation cycles are longer, and fragility higher toughness is poor, and impact resistance is poor.It is preferable that polyethylene glycol (PEG) belongs to hydrophily
Degradation material, PLLA hydrophilicity can be improved by PEG and PLLA copolymerization, and PEG can polymerize as PLLA
Initiator, form block copolymer in the way to insert, according to the proportioning of starting monomer, can conveniently design its copolymer
Structure and molecular weight.
Supercritical carbon dioxide can dissolve the nonpolar molecule and some polar molecules of most of low molecule amounts, but most of
Industrial widely used polymer can not be but dissolved under the conditions of relatively mild, only unformed fluoropolymer and silicon
Oxygen alkane polymer can be completely dissolved in supercritical carbon dioxide, therefore, and most of polymerisations in supercritical carbon dioxide are
It is heterogeneous, i.e. precipitation polymerization.There are some shortcomings in precipitation polymerization, such as conversion ratio is low, and molecular weight of product is smaller and product shape
State is irregular etc..
The content 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 block
The preparation method of PLLA-b-PEG-b-PLLA copolymers；This method can be realized scattered poly- in supercritical carbon dioxide environment
Close, the conversion ratio for improving raw material is low, the larger molecule of synthetic molecular weight, meanwhile, improve the systematicness of product molecule form.
To reach above-mentioned purpose, the invention provides the side of PLLA and PEG block copolymerization in a kind of supercritical carbon dioxide
Method, is comprised the following steps that：
S1, lactide monomer (L-LA) is dried 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
In mol ratio input reactor, stir, obtain reaction solution；Stabilizer PCL-b-PDMS-b-PCL is added into the reaction solution,
The addition of the stabilizer PCL-b-PDMS-b-PCL is 0~10wt% of the reaction solution；
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 " supercritical carbon dioxide dispersin polymerization stabilizer
And preparation method thereof good application method (ZL2013101210958) " be made.
S3, the reactor vacuumized；
This step is primarily to further remove moisture that may be present in demonomerization, catalyst and initiator.
S4、CO2Purge the reactor and the connecting line with the reactor；
This step is primarily to further remove the air and moisture in pipeline and in kettle；
S5, into the reactor it is passed through CO2Pressure reaches 16~20MPa in kettle, meanwhile, heat the reactor extremely
Temperature in the kettle reaches 80~100 DEG C；Keep pressure in the kettle, temperature-resistant, 12~48h of sustained response；
S6, using frozen water reactor is cooled to below supercritical carbon dioxide critical-temperature；
S7, pressure release to CO2Release is complete, takes out product, obtains PLLA and PEG block copolymer.
Under preferred embodiment, the mol ratio of lactide monomer described in step S2 and the polyethylene glycol is 80:20；It is described steady
The addition for determining agent PCL-b-PDMS-b-PCL is the 5wt% of the reaction solution.
Under preferred embodiment, step S5 is：CO is passed through into the reactor2Pressure reaches 18MPa in kettle, meanwhile, plus
The heat reactor to temperature in the kettle reaches 100 DEG C；Keep pressure in the kettle, temperature-resistant, sustained response 24h.
Advantage of the invention is that：
1st, the inventive method has successfully prepared the PLLA-b-PEG-b-PLLA block copolymerizations with good combination property
Product, the conversion ratio of lactide monomer can reach more than 92%, and stabilizing agent dosage only needs 3%, and the reaction time significantly reduces, reaction
Mild condition, separating-purifying need to only depressurize exclusion carbon dioxide, and technique is simple；In addition to catalyst and initiator, it has been not required to
Machine solvent, meets the direction of green chemistry；The inventive method is a kind of biomaterial synthetic method with development potentiality,
Have broad application prospects.
2nd, the inventive method successfully realizes dispersin polymerization, has been largely overcoming supercritical carbon dioxide environment
In shortcoming present in common precipitation polymerization, in the presence of stabilizer, can polymer and solvent interface formation one
Fixed active force, produces steric effect to prevent the cohesion of particle by physical absorption or chemical graft；The inventive method is improved
Reaction efficiency and yield, the inventive method can be used for polymerization polylactic acid, polycaprolactone and its copolymerization in supercritical carbon dioxide
The linear aliphatic adoption ester such as thing.
The present invention as solvent, can be such that the Biodegradable material of preparation avoids using having conventional using supercritical fluid
Organic solvent, more environmental protection, and later separation is simple, and solvent residual amount is few, and polymerisation is one in supercritical fluid
Plant the synthetic process for having good prospect.
Brief description of the drawings
Fig. 1 is PLLA-b-PEG-b-PLLA synthetic route charts；
Fig. 2 is PLLA-b-PEG-b-PLLA block copolymerization reaction experiment installation drawings in supercritical carbon dioxide；
Fig. 3 is the 1H-NMR spectrograms of PLLA-b-PEG-b-PLLA block copolymerization products；
Fig. 4 is the DSC collection of illustrative plates of PLLA-b-PEG-b-PLLA block copolymerization products.
Embodiment
The route of the PLLA in supercritical carbon dioxide and PEG block copolyreaction involved by following embodiments, such as Fig. 1
It is shown；Reaction unit involved by embodiment is：Volume 50ml is with sapphire visual window, equipped with electromagnetic stirring system sum
The autoclave (highest operating pressure 30MPa, 150 DEG C of maximum allowable operating temperature (M.A.O.T.)) of electric heating system is controlled, reactor is using it
It is preceding first to be cleaned using dichloromethane and use hot blast it is fully dried.
The process chart of reaction is as shown in Figure 2：Wherein, 1 is CO2Gas cylinder, 2 be cylinder pressure gauge, and 3 be gas cylinder valve, 4
It is cooler, 5 be plunger pump, and 6 be pressure gauge, and 7 be reactor inlet valve, and 8 be pressure gauge, and 9 be sapphire visual window, and 10 be magnetic
Power agitating device, 11 be electric heating chuck, and 12 be air bleeding valve, and 13 be heating tape, and 14 be collection device, and 15 be bleeder valve, and 16 be stream
Gauge.
PROCESS OVERVIEW of the embodiment of the present invention is：
Monomer is dried under reduced pressure at 30 DEG C in advance and removed water overnight；Reactor is cleaned using dichloromethane and use before experiment
Hot blast makes it fully dry；By monomer (L-LA), catalyst (Sn (Oct) 2) and macromole evocating agent (PEG) according to 60:0.2:
10~100:0.8:30 molar ratio is put into reactor, and it is 0~10wt% to add homemade stabilizing agent dosage；Using true
Empty pump vacuumizes to remove moisture that may be present in demonomerization, catalyst and initiator to reactor；Use CO2Purge reactor
And pipeline, remove the air and moisture in pipeline and in kettle；Outlet valve is closed, CO is passed through into reactor using plunger pump2,
Reactor is heated simultaneously, as needed adjusted pressure and temperature to setting value；Keep pressure and temperature constant, continue 12~
In 48h reaction time, then reactor is cooled to below critical-temperature using frozen water；Outlet valve is opened, slow pressure release is treated
CO2Release is complete, opens reactor, takes out product.
Below by several specific implementation examples, the present invention will be further described.
Embodiment 1
The block copolymerization dispersin polymerization of L- lactides (L-LA) and polyethylene glycol (PEG) is entered in 50ml stainless steel cauldrons
OK, as shown in Figure 2.Monomer is dried under reduced pressure at 30 DEG C in advance and removed water overnight；Before experiment reactor is cleaned using dichloromethane
And it is fully dried using hot blast；Add monomer L-LA1.6g, PEG0.4g, 0.1g (5%) stabilizer, 45mg stannous octoates
And polytetrafluoroethylene (PTFE) rotor, seal reactor.Slowly lead to CO2Heat, system is added after 5min while opening plunger pump
Pressure, reaches after experimental temperature (80 DEG C) and reaction pressure (18MPa), starts agitator；24h is reacted, stops heating and stirs, instead
Answer kettle to stir naturally and be cooled to room temperature, it is slow to deflate.Reactor is opened, white powder product, number-average molecular weight (Mn) is collected
For 12800, molecular weight distribution (PDI) is 1.18, yield 78%.
Embodiment 2
Concrete operations add monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer, 45mg octanoic acids sub- with example 2
Tin, experimental temperature (90 DEG C), reaction pressure (18MPa), reaction time 24h, product is white powder, and number-average molecular weight (Mn) is
15255, molecular weight distribution (PDI) is 1.13.Yield 88%.
Embodiment 3
Concrete operations add monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer, 45mg octanoic acids sub- with example 2
Tin, experimental temperature (100 DEG C), reaction pressure (18MPa), reaction time 24h, product is white powder, number-average molecular weight (Mn)
For 15380, molecular weight distribution (PDI) is 1.15, yield 90%.
Fig. 3 is monomer L-LA1.6g, PEG 0.4g, 0.1g (5%) stabilizer, 45mg stannous octoates, experimental temperature (90
DEG C), reaction pressure (18MPa), reaction time 24h, the 1H-NMR spectrograms of PLLA-b-PEG-b-PLLA block copolymerization products.Position
Peak more sharp is the characteristic peak of-CH3 repeat units in PLLA at 1.5ppm, and the peak at 5.2ppm is right for-CH-
The peak answered, both combines the presence for having PLLA in provable product；Unimodal at 3.6ppm be for O-CH2-CH2-O-
The characteristic peak of ethylene glycol repetitive structure, the peak is the conclusive evidence that there is PEG in construction unit；And it is micro- at 4.3ppm
Structure corresponding to weak peak is-COOCH2-C-, and the presence or absence at the peak decides whether copolymerization occurs, and peak value is PEG at this
With the peak value of PLLA building blocks junction, at this peak value exist explanation product for PEG and PLLA block copolymer rather than
PLLA and PEG blend, can be concluded that in experiment by Fig. 3 and has synthesized subject copolymers.
Fig. 4 is the DSC collection of illustrative plates of PLLA-b-PEG-b-PLLA block copolymerization products.PLLA-b-PEG-b- in comparison diagram
PLLA and PLLA DSC plot can significantly see the two thermal physical characteristic qualitative difference.It is bright that copolymer has two comparisons
Aobvious peak, respectively positioned at 125 DEG C and 150 DEG C or so, it represents PEG and PLLA melting peak respectively, and simple PLLA
Melting peak is about about 160 DEG C, and the introducing of PEG chain segment destroys the regularity of its segment to a certain extent in PLLA structures,
So that its crystal property declines, heat endurance also occurs in that obvious decrease therewith.The melting temperature of PLLA segments occurs slight
Decline, its reason be likely due to single PLLA segments length declined caused by heat endurance occur in that down
Drop.Two kinds of polymer occurs without the peak corresponding to obvious glass transition temperature in DSC curve, thus illustrates two kinds of productions
Preferably, the isotactic characteristic of product is good for the crystal property of thing.
In the inventive method, temperature influences notable to the conversion ratio of product, and with the raising of temperature, the conversion ratio of product has
The trend significantly improved, while molecular weight of product is also with raising, especially temperature is more bright when by being increased to 90 DEG C for 80 DEG C
It is aobvious.The polymerization of 1H-NMR analytical proofs has obtained the clear and definite three block PLLA-b-PEG-b-PLLA copolymers of structure.DSC and TGA shows
Show that the thermophysical property of the product after modification by copolymerization there occurs obvious change, PLLA-b-PEG-b-PLLA is molten relative to PLLA
Point occurs in that obvious decline.Granularmetric analysis shown with the increase of PEG content in copolymer, the average grain diameter of product and
Particle size distribution range occurs in that obvious increase tendency, and this is product in reaction temperature mainly due to the reduction of melting temperature
Under softened and adhered to.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (2)
1. PLLA and the method for PEG block copolymerization in a kind of supercritical carbon dioxide, it is characterised in that comprise the following steps that：
S1, lactide monomer is dried 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 mol ratio input
In reactor, stir, obtain reaction solution；Stabilizer PCL-b-PDMS-b-PCL, the stabilizer are added into the reaction solution
PCL-b-PDMS-b-PCL addition is 0~10wt% of the reaction solution；
S3, the reactor vacuumized；
S4、CO2Purge the reactor and the connecting line with the reactor；
S5, into the reactor it is passed through CO2Pressure reaches 18MPa in kettle, meanwhile, the reactor is heated to temperature in the kettle
Reach 100 DEG C；Keep pressure in the kettle, temperature-resistant, sustained response 24h；
S6, using frozen water reactor is cooled to below supercritical carbon dioxide critical-temperature；
S7, pressure release to CO2Release is complete, takes out product, obtains PLLA and PEG block copolymer.
2. PLLA and the method for PEG block copolymerization in supercritical carbon dioxide according to claim 1, it is characterised in that step
Lactide monomer and the mol ratio of the polyethylene glycol are 80 described in rapid S2:20；The stabilizer PCL-b-PDMS-b-PCL
Addition be the reaction solution 5wt%.
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| 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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