CN105368023B - Supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof - Google Patents
Supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to bio-based, biodegradable technical field of polymer materials, it is desirable to provide supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof.The supermolecule stereoblock polylactic acid of the easy Stereocomplex crystallization is made up of elementary cell, elementary cell is the linear Poly-L-lactic acid of both-end functionalization, dextrorotation polylactic acid, or three three-arm star-shaped Poly-L-lactic acid of end functionalization, dextrorotation polylactic acid, and the end group of elementary cell is 2 urea groups 4 [1H] the pyrimidine ketone groups that can form Quadrupolar hydrogen bond；The preparation method includes prepared by step UPy end functionalization PLLA and the preparation of PDLA, the blending of PLLA/PDLA supermolecule Stereoblock polymers.The present invention is prepared for supermolecule stereoblock PLA with higher Stereocomplex crystallizing power and degree of crystallinity, and crystallization rate faster, effectively increases the heat resistance of PLA, while can also improve its solvent resistance and hydrolytic resistance.
Description
Technical field
The present invention is with regard to bio-based, biodegradable technical field of polymer materials, more particularly to easy Stereocomplex
Supermolecule stereoblock polylactic acid of crystallization and preparation method thereof.
Background technology
Supermolecule is referred to
Close the ordered molecular complex for being formed.The supramolecular degree of polymerization depends on the concentration of the construction unit of supermolecule (oligomer) and forms
Close constant.Due to special structure and performance, new causes the wide of researcher based on the supermolecule polymer of multiple hydrogen bonding
General concern.Wherein, -4 [1H]-pyrimidone (UPy) group preparation method of 2- urea groups is simple, can self-identifying formed there is height to select
Property and the AADD-DDAA type Quadrupolar hydrogen bonds of directivity, in chloroform, toluene dimeric binding constant respectively up to 6 ×
107M-1、6×108M-1, bonding force compensate for the not enough shortcoming of non-covalent bond intensity, is that supramolecular design is carried close to covalent bond
Important means are supplied.By post polymerization method, effectively UPy groups can be introduced to hydroxyl or amino-terminated polymer
In, so as to can effectively prepare supermolecule polymer.The small molecule of UPy modified with functional group or oligomer, such as polysiloxanes, polyethers,
Merlon, polyester and TPO, can assemble to form long-chain supermolecule by multiple hydrogen bonding.Due to the introducing of UPy functional groups,
The mechanical performance of these polymer, melt rheological property, machinability significantly improve.Based on polystyrene, polyacrylate,
The supermolecule of the UPy such as polymethacrylates, polyisoprene modifications has been applied to the aspects such as electrostatic spinning, surface modification.Logical
The regulation and control of module unitss are crossed, constructing for the functional material such as photoelectricity and intellectual material is also can achieve.
Polylactic acid (PLA) is a kind of synthesis macromolecular material with excellent biocompatibility and biodegradability, right
Environmental friendliness, nonhazardouss, can be applicable to the bio-medicals such as packaging, fibrous material field, and organizational project, medicament slow release neck
Domain, can substitute conventional petroleum based polyalcohol as environment-friendly materials.PLA has two kinds of enantiomer-specific structures, i.e. Poly-L-lactic acid
And dextrorotation polylactic acid (PDLA) (PLLA).When PLLA and PDLA is blended, Stereocomplex crystallization can be formed, its fusing point is up to 230
DEG C, about 50 DEG C are improved with the homogeneity crystalline phase ratio of independent PLLA or PDLA.Compared with homogeneity crystallization PLA material, PLA Stereocomplexes
Crystalline material has high-melting-point, high intensity, high-moduluss and excellent solvent resistant, hydrolytic Resistance.Therefore, Stereocomplex is crystallized is
The effective way of PLA combination properties is improved, most important to widening its industrial application.
But the preparation of high heat-resisting PLA Stereocomplexes crystalline material is more difficult.In PLLA/PDLA co-mixing systems, there is homogeneity
Crystallization and the competition of Stereocomplex crystallization.Only as the molecular weight of PLLA and PDLA relatively low (＜ 20kg/mol), just it is easier to
Form dystectic Stereocomplex crystallization.When PLLA and PDLA molecular weight is larger (weight average molecular weight ＞ 40kg/mol), logical
The homogeneity crystallization of low melting point is often primarily formed in crystallization process.But the mechanical performance and machinability of low-molecular-weight PLA are poor, it is impossible to
It is directly used as plastics use.Therefore, promote the Stereocomplex crystallization of high molecular (＞ 40kg/mol) PLA and prepare high molecular
Stereocomplex crystalline material significant to the combination property for improving PLA.
High molecular PLLA and PDLA co-mixing systems be difficult to Stereocomplex crystallization main cause be its stereoisomerism chain it
Between interaction too weak.Yui etc. (Makromol.Chem.1990,191,481) and Han etc. (J.Phys.Chem.B 2015,
doi：10.1021/acs.jpcb.5b06757) once reporting make PLLA and PDLA chains intersegmental by covalent bond phase using block copolymerization
Even, the interaction between stereoisomerism chain is enhanced, so as to effectively facilitate its Stereocomplex crystallization.But in the stereoblock
In copolymer, the degree of freedom of PLLA and PDLA blocks is restricted, and the dissolubility of Stereoblock polymers is poor.In addition,
Multiple hydrogen bonding bonding based on UPy groups is a kind of effective means for preparing supermolecule polymer and block copolymer.By UPy bases
Group is introduced to the supermolecule Stereoblock polymers that can prepare PLA in PLLA and PDLA strands.Many heavy hydrogen between UPy groups
Key effect will improve the intersegmental interaction of PLLA and PDLA chains and degree of scatter, so as to be conducive to its Stereocomplex crystallization.Separately
Outward, relative to the Stereoblock polymers of covalent bonding, supermolecule Stereoblock polymers can be obtained by simple blending method
Arrive, preparation method is simple.
Patent " polylactic acid of Stereocomplex crystallization control/hydrogenated butadiene polymer supermolecule elastomer " (application number
CN2015103999568) (wherein PEB in PLLA-PEB-PLLA the and PDLA-PEB-PDLA blends of UPy bondings has been reported in
Random copolymer for ethylene/butylene), Stereocomplex crystallization is easily formed, and can obtain the PLA/PEB that hard area is crystallized containing Stereocomplex
Supermolecule elastomer, but the molecular weight (≤4800g/mol) of PLLA and PDLA blocks in such blends, and molecular weight compared with
Little PLLA and PDLA copolymers inherently easily Stereocomplex crystallization (Pan etc., J.Phys.Chem.B 2015,119,6462),
In the presence of without soft section PEB, the PLLA/PDLA blending materials of the small-molecular-weight are crisp, it is difficult to process, intensity is extremely low.Therefore, promote
The Stereocomplex of high molecular PLLA and PDLA systems is crystallized more actual application value.
Content of the invention
Present invention is primarily targeted at overcoming deficiency of the prior art, there is provided a kind of oversubscription of easy Stereocomplex crystallization
Sub- stereoblock PLA and preparation method thereof.For solving above-mentioned technical problem, the solution of the present invention is：
Supermolecule stereoblock polylactic acid (PLA) of easy Stereocomplex crystallization is provided, is made up of elementary cell, described basic
Unit is the linear Poly-L-lactic acid (PLLA) of both-end functionalization, dextrorotation polylactic acid (PDLA), or the three of three end functionalizations
Arm star Poly-L-lactic acid (PLLA), dextrorotation polylactic acid (PDLA), and the end group of elementary cell is the 2- that can form Quadrupolar hydrogen bond
- 4 [1H]-pyrimidone (UPy) group of urea groups；
The linear Poly-L-lactic acid of the both-end UPy modifications, dextrorotation polylactic acid have following structure：
Wherein, n is 150～900；
The three-arm star-shaped Poly-L-lactic acid of the three ends UPy modifications, dextrorotation polylactic acid have following structure：
Wherein, n is 100～600.
Method for preparing the supermolecule stereoblock polylactic acid of the easy Stereocomplex crystallization is provided, is specifically included down
State step：
(1) preparation of UPy ends functionalization PLLA and PDLA：
Hydroxy-end capped PLA and UPy-NCO is added in uncommon Dinke pipe, evacuation 1h under the conditions of 65 DEG C, then carry out three
It is finally argon atmosphere that secondary gas displacement is made in uncommon Dinke pipe；Stannous octoate, and the toluene for drying is added in uncommon Dinke pipe
Or DMF (DMF), 6～48h of stirring reaction at 90～120 DEG C；React after terminating using Rotary Evaporators
Organic solvent is removed, is dissolved during then add the product for obtaining to dichloromethane or chloroform, filtered；At room temperature
Solvent is made to volatilize, the solid matter for obtaining is the PLA, the i.e. PLLA and PDLA of UPy ends functionalization of UPy ends functionalization；Then
6h is vacuum dried under the conditions of 70 DEG C, standby；
Wherein, the PLA is the linear PLLA of two-arm, two-arm linear PDLA, the PLLA of three-arm star-shaped or three arm stars
The PDLA of shape；
The consumption of each reactant is：The mol ratio of hydroxy-end capped PLA and UPy-NCO is 1: 5～1: 30；Reaction dissolvent first
The interpolation quality of benzene or DMF is 20～40 times that PLA adds quality；Stannous octoate add quality be PLA add quality 0.4～
10‰；
(2) prepared by the blending of PLLA/PDLA supermolecules Stereoblock polymers：
The PLLA and PDLA of the UPy ends functionalization that step (1) is prepared, is dissolved in chloroform, makes polymer solution
Concentration is 50g/L, and PLLA and PDLA mixing qualities ratio is 1: 9～9: 1；After being uniformly mixed, polymer solution is cast
In politef culture dish, make solvent volatilize completely at room temperature, then politef culture dish is put into 70 DEG C true
6h is dried in empty baking oven, that is, obtain supermolecule stereoblock PLA of easy Stereocomplex crystallization；
Wherein, linear PLL A and PDLA, Huo Zhesan of the PLLA and PDLA of UPy ends functionalization using both-end UPy functionalizations
Three-arm star-shaped PLLA of end UPy functionalizations and PDLA.
Compared with prior art, the invention has the beneficial effects as follows：
1st, the present invention in using bonding force strong can self-identifying formed Quadrupolar hydrogen bond interact UPy groups as structure list
Unit is prepared for supermolecule stereoblock PLA.Compared with the PLLA/PDLA co-mixing systems of similar mass, the supermolecule solid is embedding
Section PLA has higher Stereocomplex crystallizing power and degree of crystallinity, and crystallization rate faster.Effectively increase the resistance to of PLA
Hot property, while can also improve its solvent resistance and hydrolytic resistance；
2nd, PLA material prepared by the present invention carrys out authigenic material Renewable resource, can be degradable for carbon dioxide after use
And water, environmental protection, the pollution produced by environment are little；
3rd, high molecular PLA stereoscopic composite material of the present invention is prepared using blending method, and method is simple, low cost.
Description of the drawings
Fig. 1 is the DSC heating curves (10 DEG C/min) of embodiment 11 and the melting qtenched sample of comparative example 3.
Fig. 2 is DSC heating curve of the embodiment 11 with 3 sample of comparative example after isothermal melting crystallization under the conditions of 140 DEG C
(10℃/min).
The WAXD curves that Fig. 3 is surveyed with 3 sample of comparative example after isothermal melting crystallization under the conditions of 140 DEG C by embodiment 11.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
The professional and technical personnel that the following examples can make this professional is more fully understood the present invention, but not with any side
Formula limits the present invention.
It is as follows with medicine that the present invention prepares used reagent：L- lactides and D- lactides are purchased from Purao AS, through second
Recrystallization after acetoacetic ester dissolving, standby；Octoate catalyst stannous are purchased from Sigma companies；1,6 hexanediol is purchased from Tokyo chemical conversion industry
Co., Ltd.；Trimethylolpropane is purchased from Aladdin company.
The structural formula of UPy-NCO of the present invention is：
UPy-NCO according to document (Sontjens et al.Macromolecules, 2008,41：5703-5708) described
Prepared by method, comprise the following steps that：During 2- amino-4-hydroxies -6- methylpyrimidines (10.0g) is added to 500ml there-necked flasks,
Evacuation 0.5h at 65 DEG C, argon filling gas shielded add 95.0g hexamethylene diisocyanates (HDI) and 3.2g crassitudes
Ketone is catalyst, wherein 7 times for 2- amino-4-hydroxy -6- methylpyrimidine molal quantitys of HDI molal quantitys, and catalyst content is total
The 3% of reactant quality.At 100 DEG C after reaction 16h, product is dissolved in chloroform, instills the normal heptane that volume ratio is for 6: 1
With (common 700ml) in the mixed liquor of diisopropyl ether, precipitation, filter.White solid product is placed in 50 DEG C of vacuum drying ovens and is dried
10h, standby.
Three-arm star-shaped PLLA, PDLA of the hydroxy-end capped linear and three terminal hydroxy groups end-blocking of both-end used by of the invention pass through L- or
The ring-opening polymerisation self-control of D- lactides.Design molecular weight is concrete for three-arm star-shaped PLLA of the three terminal hydroxy groups end-blocking of 60kg/mol
Preparation process is as follows：Flask is added after 30g L- lactides, 0.067g trimethylolpropanes and 0.09g stannous octoates are dried
In, argon is protected, and reacts 5h, obtain PLLA products under the conditions of 130 DEG C.The crude product for obtaining is dissolved in chloroform,
In dehydrated alcohol, precipitation removes unreacted lactide, filters, is dried to obtain polymer.By changing initiator and lactide
Mass ratio, be prepared for the polymer with different molecular weight.The molecular weight of polymer, molecular weight distributing index (PDI) are by coagulating
Glue penetration chromatograph (GPC) is determined.The three-arm star-shaped of the hydroxy-end capped linear and three terminal hydroxy groups end-blocking of both-end used herein
The preparation condition and molecular weight of PLLA, PDLA is listed in table 1.
Table 1：Both-end hydroxy-end capped linear and three terminal hydroxy groups end-blocking three-arm star-shaped PLLA, PDLA preparation condition with point
Son amount
In polymer name, 2L, 2D, 3L, 3D represent hydroxy-end capped linear PLL A, PDLA of both-end and three terminal hydroxy groups respectively
Three-arm star-shaped PLLA, PDLA of end-blocking, suffix numeral represent the weight average molecular weight of polymer.
Molecular weight is tested：Molecular weight of copolymer distribution is determined using Waters chromatograph of gel permeation, and test temperature is 30
DEG C, mobile phase is tetrahydrofuran, and standard sample is monodisperse polystyrene.
1) preparation of UPy ends functionalization PLLA and PDLA
In following embodiment 1～8, by the three-arm star-shaped of the hydroxy-end capped linear and three terminal hydroxy groups end-blocking of both-end
The reaction of PLLA, PDLA and UPy-NCO, is prepared for the three-arm star-shaped of the linear and three end UPy functionalizations of both-end UPy functionalizations
PLLA, PDLA, specific as follows：
After hydroxy-end capped PLA, UPy-NCO is added in uncommon Dinke pipe, evacuation 1h under the conditions of 65 DEG C.Carry out three times
It is finally argon atmosphere that gas displacement is made in uncommon Dinke pipe；To in uncommon Dinke pipe add stannous octoate, and dry toluene or
DMF, 6～48h of stirring reaction at 90～120 DEG C；Reaction removes organic solvent using Rotary Evaporators after terminating, and is subsequently adding
Dissolve into dichloromethane, filter.Solvent is made to volatilize at room temperature, the solid matter for obtaining is the PLA of UPy ends functionalization.
6h is vacuum dried under the conditions of 70 DEG C, standby.Wherein, the mol ratio of PLA and UPy-NCO is 1: 5～1: 30.Toluene or DMF
Interpolation quality be 20～40 times of PLA mass, stannous octoate adds quality for 0.4～the 10 ‰ of PLA mass.
Utilize1H NMR determine the terminal hydroxy group response rate of PLA.Test temperature is room temperature, and solvent is deuterochloroform, chemistry
Displacement is corrected by solvent peak.It is that the formant at 0.43ppm represents the secondary first in the lactic acid units of PLA ends in chemical shift
The proton resonance peak of base, is the proton resonance peak that the formant at 13.1ppm represents amido in UPy in chemical shift.According to PLA
In main chain on the basis of the area at the methine protons peak of lactic acid units, the terminal hydroxy group response rate of PLA is obtained.
Table 2：The preparation of the linear of UPy ends functionalization, three-arm star-shaped PLLA and PDLA
In polymer name, 2L-U, 2D-U, 3L-U, 3D-U represent respectively both-end UPy end-blocking linear PLL A, PDLA and
Three-arm star-shaped PLLA, PDLA of three end UPy end-blockings, suffix numeral represent the weight average molecular weight of polymer.
As shown in Table 2, in the PLLA and PDLA for preparing UPy ends functionalization, when reacted between for 16h when, the end hydroxyl of PLA
Base response rate is higher, more than 85%.
2) prepared by the blending of supermolecule stereoblock PLA
Embodiment 9～13
The PLLA and PDLA of the UPy ends functionalization of certain mass ratio are dissolved in chloroform, the concentration for making polymer solution is
50g/L, after being uniformly mixed, polymer solution is poured and is cast from politef culture dish；Make solvent complete at room temperature
Volatilization, then politef culture dish is put in 70 DEG C of vacuum drying oven and dries 6h, that is, obtain the super of easy Stereocomplex crystallization
Molecular stereo block PLA.
Comparative example 1～5
The PLLA and PDLA of the hydroxyl terminal functionalization of certain mass ratio are dissolved in chloroform, the concentration of polymer solution is
50g/L, after being uniformly mixed, polymer solution is poured and is cast from politef culture dish, then make solvent complete under room temperature
Complete volatilize, then politef culture dish is put in 60 DEG C of vacuum drying oven and dries 6h.
The test of crystallization behavior：Tested using DSC, nitrogen atmosphere.Non-isothermal cold crystallization test in, sample with 50 DEG C/
Min is kept 2min to eliminate thermal history, is then cooled to 0 DEG C with 100 DEG C/min, keep at 0 DEG C from room temperature to 250 DEG C
After 3min, then 250 DEG C are warming up to 10 DEG C/min.In isothermal melting crystallization test, sample is with 50 DEG C/min from room temperature
To 250 DEG C, 2min is kept to eliminate thermal history, then with 100 DEG C/min fast coolings to set test temperature, kept for one section
Time is fully crystallized polymer, then is warming up to 250 DEG C with 10 DEG C/min and detects its melting behavior.
Crystallization kineticses are calculated with Thermal Parameter：In the 10 DEG C/min temperature-rise periods after non-isothermal cold crystallization, 140
DEG C to the melting peak that the endothermic peak between 180 DEG C is the crystallization of PLLA, PDLA homogeneity, peak temperature is homogeneity crystalline melt point (TM, hc),
Integral area is that homogeneity crystallizes melting enthalpy (Δ HM, hc).Endothermic peak between 180 to 240 DEG C is that the vertical structure of PLLA/PDLA blends is multiple
The melting peak of crystallization is closed, peak temperature is Stereocomplex crystalline melt point (TM, sc), integral area is Stereocomplex crystallization enthalpy (Δ
HM, sc).Relative fractions (the f of Stereocomplex crystallizationsc) by formula fsc=Δ HM, sc/(ΔHM, sc+ΔHM, hc) be calculated.It is based on
The data of isothermal melting crystallization, flexible chain (t0.5) obtained by Avrami Equation for Calculating, concrete grammar reference literature ACS
Applied Materials＆Interfaces, 2009, Isosorbide-5-Nitrae 02.Wherein, hc represents homogeneity crystallization, and sc represents Stereocomplex knot
Brilliant.
Crystalline texture and the crystal formation that blend is analyzed using wide-angle X ray diffractor (WAXD).Non- UPy is modified PLLA/
PDLA blends melt 2min in hot press with the supermolecule Stereoblock polymers of UPy modifications and eliminate thermal history at 250 DEG C,
Certain thickness thin slice is pressed into, then fast transfer was allowed to be fully crystallized to isothermal crystal certain time in 140 DEG C of baking ovens,
And by crystallization after thin slice carry out WAXD analyses.
The melting qtenched sample of embodiment 9～13 and comparative example 1～5 is hot in non-isothermal cold crystallization and melting process
As shown in table 3, wherein heating rate is 10 DEG C/min to energy parameter.
Table 3：The melting qtenched sample of embodiment 9～13 and comparative example 1～5 is in non-isothermal cold crystallization and melting process
Thermal Parameter
From table 3 and Fig. 1：For hydroxy-end capped PLLA and the PDLA systems of equal quality ratio blending, its vertical structure is multiple
The melting enthalpy and its relative amount for closing crystallization is less, and the homogeneity crystallization for primarily forming low melting point in co-mixing system is described.Work as PLLA
When being more than 85kg/mol with the weight average molecular weight of PDLA, its Stereocomplex crystallization relative amount is less than 20%.For being blocked by UPy
Linear and three-arm star-shaped equivalent PLLA, PDLA composition supermolecule Stereoblock polymers, primarily form in temperature-rise period
Dystectic Stereocomplex crystallization.Although there is homogeneity crystallization and Stereocomplex knot simultaneously in temperature-rise period in embodiment 9,11 samples
Brilliant melting peak, but compared with comparative example 1,3, the content of its Stereocomplex crystallization is significantly increased.Comparing embodiment 9,10 can
Know, the supermolecule Stereoblock polymers constituted by more three-arm star-shaped PLLA of UPy group contents and PDLA are more likely formed vertical
Structure compound crystal.Comparing embodiment 12,13 and comparative example 4,5 understand, for the PLLA/PDLA systems of non-equal quality ratio, lead to
Cross UPy groups construct supermolecule Stereoblock polymers can also effectively improve material crystallization rate and Stereocomplex crystallization contain
Amount.
Table 4：Embodiment 9～11 and 1～3 sample of comparative example 140 DEG C of isothermal meltings crystallize and temperature-rise period in power
Learn and Thermal Parameter
From table 4 and Fig. 2,3, the supermolecule Stereoblock polymers containing UPy groups are in isothermal melting crystallization process
Primarily form dystectic Stereocomplex crystallization.For the PLLA/PDLA co-mixing systems of terminal hydroxy group modification, crystallize in isothermal melting
In simultaneously form homogeneity crystallization and crystallize with Stereocomplex, and homogeneity crystallization is dominant.In addition, containing UPy groups in embodiment 9～11
The t of supermolecule Stereoblock polymers0.5Substantially less than 1～3 sample of comparative example.The result card of these non-isothermals and isothermal crystal
Understand that the PLLA/PDLA supermolecule Stereoblock polymers formed by strong Quadrupolar hydrogen bond interaction between UPy groups are significantly carried
The high content of the Stereocomplex crystallizing power of PLA and Stereocomplex crystallization, while also improve its crystallization rate.
For further confirming that the PLLA/PDLA supermolecule Stereoblock polymers in the present invention containing UPy groups are conducive to shape
Structure compound crystal is set up, WAXD tests are carried out to 140 DEG C isothermal melting crystallized sample of the example 11 with comparative example 3.Can by Fig. 3
Know：11 diffraction maximums for assuming Stereocomplex crystallization of embodiment, and occur the homogeneity crystallization of PLA in comparative example 3 simultaneously and found structure
The diffraction maximum of compound crystal, and the diffraction maximum of homogeneity crystallization is stronger.In Fig. 3, sc represents Stereocomplex crystallization, and hc represents homojunction
Brilliant.
Finally it should be noted that listed above is only specific embodiment of the invention.It is clear that the invention is not restricted to
Above example, can also have many variations.One of ordinary skill in the art can be directly led from present disclosure
The all deformations for going out or associating, are considered as protection scope of the present invention.
Claims (2)
1. the supermolecule stereoblock polylactic acid of easy Stereocomplex crystallization, is made up of elementary cell, it is characterised in that described basic
Unit is the linear Poly-L-lactic acid of both-end functionalization, dextrorotation polylactic acid, or the three-arm star-shaped of three end functionalizations is left-handed poly-
Lactic acid, dextrorotation polylactic acid, and the end group of elementary cell is -4 [the 1H]-pyrimidine ketone groups of 2- urea groups that can form Quadrupolar hydrogen bond；
The linear Poly-L-lactic acid of the both-end UPy modifications, dextrorotation polylactic acid have following structure：
Wherein, n is 150～900；
The three-arm star-shaped Poly-L-lactic acid of the three ends UPy modifications, dextrorotation polylactic acid have following structure：
Wherein, n is 100～600.
2. the method for being used for preparing the supermolecule stereoblock polylactic acid of easy Stereocomplex crystallization described in claim 1, its feature
It is, specifically includes following step：
(1) preparation of UPy ends functionalization PLLA and PDLA：
Hydroxy-end capped PLA and UPy-NCO is added in uncommon Dinke pipe, evacuation 1h under the conditions of 65 DEG C, then carry out three gas
It is finally argon atmosphere that body displacement is made in uncommon Dinke pipe；Stannous octoate, and dry toluene or N is added in uncommon Dinke pipe,
Dinethylformamide, 6～48h of stirring reaction at 90～120 DEG C；Reaction is removed organic molten using Rotary Evaporators after terminating
Agent, dissolves during then add the product for obtaining to dichloromethane or chloroform, and filters；Wave solvent at room temperature
Send out, the solid matter for obtaining is the PLA, the i.e. PLLA and PDLA of UPy ends functionalization of UPy ends functionalization；Then in 70 DEG C of bars
6h is vacuum dried under part, standby；
Wherein, the PLA is the linear PLLA of two-arm, two-arm linear PDLA, the PLLA of three-arm star-shaped or three-arm star-shaped
PDLA；
The consumption of each reactant is：The mol ratio of hydroxy-end capped PLA and UPy-NCO is 1: 5～1: 30；Reaction dissolvent toluene or
The interpolation quality of DMF is 20～40 times that PLA adds quality；Stannous octoate add quality be PLA add quality 0.4～
10‰；
(2) prepared by the blending of PLLA/PDLA supermolecules Stereoblock polymers：
The PLLA and PDLA of the UPy ends functionalization that step (1) is prepared, is dissolved in chloroform, makes the concentration of polymer solution
For 50g/L, and the PLLA and PDLA mixing quality ratio of UPy ends functionalization is 1: 9～9: 1；After being uniformly mixed, by polymer
Solution-cast makes solvent volatilize completely in politef culture dish, at room temperature, then politef culture dish is put into
6h is dried in 70 DEG C of vacuum drying oven, that is, obtain supermolecule stereoblock PLA of easy Stereocomplex crystallization；
Wherein, linear PLL A and PDLA of the PLLA and PDLA of UPy ends functionalization using both-end UPy functionalizations, or three end UPy
Three-arm star-shaped PLLA of functionalization and PDLA.
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| JP2008248176A (en) * | 2007-03-30 | 2008-10-16 | Teijin Ltd | Method for producing stereocomplex polylactic acid |
| CN104650548B (en) * | 2015-02-05 | 2016-08-24 | 浙江大学 | The easily preparation method of the poly-lactic acid in high molecular weight material of Stereocomplex crystallization |
| CN105017779A (en) * | 2015-07-06 | 2015-11-04 | 浙江大学 | Steric compound crystal controlled polylactic acid/hydrogenated polybutadiene supermolecular elastomer |
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