CN105368023A - Easy stereo-complex crystal supramolecular stereoblock polylactic acid and preparation method thereof - Google Patents
Easy stereo-complex crystal supramolecular stereoblock polylactic acid and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the bio-based biodegradable polymer material technical field, and aims to provide easy stereo-complex crystal supramolecular stereoblock polylactic acid and a preparation method thereof. The easy stereo-complex crystal supramolecular stereoblock polylactic acid comprises a basic unit, the basic unit is double-end-functionalized linear poly-L-lactic acid(PLLA) and poly-D-lactic acid(PDLA), or three-end-functionalized three-arm star-shaped poly-L-lactic acid and poly-D-lactic acid, the terminal group of the basic unit is 2-ureido-4 [1H]-pyrimidinone group capable of forming a quadruple hydrogen bond, the preparation method comprises the steps of preparing of UPy-end-functionalized poly-L-lactic acid and poly-D-lactic acid and preparing of PLLA / PDLA supramolecular stereoblock polymer by blending. The supramolecular stereoblock PLA prepared by the method has high stereocomplex crystallization capacity, crystallinity, and faster crystallization rate, the PLA heat resistance is effectively improved, and meanwhile the solvent resistance and hydrolysis resistance can be improved.
Description
Technical field
The invention relates to bio-based, biodegradable technical field of polymer materials, supramolecule stereoblock poly(lactic acid) of particularly easy Stereocomplex crystallization and preparation method thereof.
Background technology
Supramolecule is referred to and to be associated the ordered molecular complex body formed by non-covalent interactions such as complementary hydrogen bond, Van der Waals force, π-pi-conjugated between molecule.The supramolecular polymerization degree depends on concentration and the association constant of the construction unit of supramolecule (oligopolymer).Due to special structure and performance, the novel supermolecule polymer based on multiple hydrogen bonding causes the extensive concern of investigator.Wherein, preparation method is simple for 2-urea groups-4 [1H]-pyrimidone (UPy) group, self-identifying can form the AADD-DDAA type Quadrupolar hydrogen bond with high selectivity and directivity, in trichloromethane, toluene, dimeric binding constant reaches 6 × 10 respectively
7m
-1, 6 × 10
8m
-1, linkage force, close to covalent linkage, compensate for the shortcoming of non covalent bond undercapacity, for supramolecular design provides important means.By post polymerization method, effectively UPy group can be introduced into in hydroxyl or amino-terminated polymkeric substance, thus effectively can prepare supermolecule polymer.The small molecules of UPy modified with functional group or oligopolymer, as polysiloxane, polyethers, polycarbonate, polyester and polyolefins, form long-chain supramolecule by multiple hydrogen bonding assembling.Due to the introducing of UPy functional group, the mechanical property of these polymkeric substance, melt rheological property, workability significantly improve.The supramolecule modified based on UPy such as polystyrene, polyacrylic ester, polymethacrylate, polyisoprene has been applied to the aspect such as electrostatic spinning, surface modification.By the regulation and control of assembled unit, also constructing of the functional materials such as photoelectricity and intelligent material can be realized.
Poly(lactic acid) (PLA) is a kind of synthesized polymer material with excellent biocompatibility and biodegradability, environmentally friendly, toxicological harmless, can be applicable to packaging, filamentary material field, and the bio-medical such as organizational project, medicament slow release field, can be used as environment-friendly materials and substitute conventional petroleum based polyalcohol.PLA has two kinds of enantiomer-specific structures, i.e. Poly-L-lactic acid (PLLA) and dextrorotation poly(lactic acid) (PDLA).When PLLA and PDLA is blended, Stereocomplex crystallization can be formed, its fusing point up to 230 DEG C, with the homojunction crystalline phase of independent PLLA or PDLA than improving about 50 DEG C.Compared with homogeneity crystallization PLA material, PLA Stereocomplex crystalline material has solvent resistant, the resistant to hydrolysis performance of high-melting-point, high strength, high-modulus and excellence.Therefore, Stereocomplex crystallization is the effective way improving PLA over-all properties, and to widening, its industrial application is most important.
But the preparation of high heat-resisting PLA Stereocomplex crystalline material is more difficult.In PLLA/PDLA co-mixing system, there is the competition of homogeneity crystallization and Stereocomplex crystallization.When only having molecular weight all lower (the < 20kg/mol) as PLLA and PDLA, just comparatively easily form dystectic Stereocomplex crystallization.When PLLA and PDLA molecular weight is larger (weight-average molecular weight > 40kg/mol), the main homogeneity crystallization forming low melting point in usual crystallisation process.But the mechanical property of lower molecular weight PLA and workability poor, can not be directly used as plastics use.Therefore, promote that the Stereocomplex crystalline material of the Stereocomplex crystallization of high molecular (> 40kg/mol) PLA and preparation high molecular is significant to the over-all properties improving PLA.
The major cause that high molecular PLLA and PDLA co-mixing system are difficult to Stereocomplex crystallization is that the interaction between its stereoisomerism chain is too weak.(the Makromol.Chem.1990 such as Yui, 191,481) and (J.Phys.Chem.B2015 such as Han, doi:10.1021/acs.jpcb.5b06757) once report utilize block copolymerization to make PLLA with PDLA chain is intersegmental is connected by covalent linkage, enhance the interaction between stereoisomerism chain, thus effectively can promote its Stereocomplex crystallization.But in this Stereoblock polymers, the degree of freedom of PLLA and PDLA block is restricted, and the solvability of Stereoblock polymers is poor.In addition, the multiple hydrogen bonding bonding based on UPy group is a kind of effective means preparing supermolecule polymer and segmented copolymer.UPy group is introduced in PLLA and PDLA molecular chain, the supramolecule Stereoblock polymers of PLA can be prepared.Multiple hydrogen bonding effect between UPy group will improve the intersegmental interaction of PLLA and PDLA chain and degree of scatter, thus is conducive to its Stereocomplex crystallization.In addition, relative to the Stereoblock polymers of covalent bonding, supramolecule Stereoblock polymers obtains by simple blending method, and preparation method is easy.
Patent " poly(lactic acid)/hydrogenated butadiene polymer supramolecule elastomerics of Stereocomplex crystallization control " (application number CN2015103999568) has been reported in (wherein PEB is the random copolymers of ethylene/butylene) in PLLA-PEB-PLLA and the PDLA-PEB-PDLA blend of UPy bonding, the crystallization of easy formation Stereocomplex, the PLA/PEB supramolecule elastomerics containing Stereocomplex crystallization hard area can be obtained, but the molecular weight (≤4800g/mol) of PLLA and PDLA block in such blends, and PLLA and the PDLA multipolymer of molecular weight inherently easy Stereocomplex crystallization (Pan etc., J.Phys.Chem.B2015, 119, 6462), when existing without soft section of PEB, the blended material of PLLA/PDLA of this small-molecular-weight is crisp, be difficult to processing, intensity is extremely low.Therefore, promote that the Stereocomplex crystallization of high molecular PLLA and PDLA system will have more actual application value.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provides supramolecule stereoblock PLA of a kind of easy Stereocomplex crystallization and preparation method thereof.For solving the problems of the technologies described above, solution of the present invention is:
The supramolecule stereoblock poly(lactic acid) (PLA) of easy Stereocomplex crystallization is provided, be made up of elementary cell, described elementary cell is functionalized linear Poly-L-lactic acid (PLLA), the dextrorotation poly(lactic acid) (PDLA) of both-end, or functionalized three arm star Poly-L-lactic acid (PLLA), the dextrorotation poly(lactic acid) (PDLA) of three ends, and the end group of elementary cell is 2-urea groups-4 [1H]-pyrimidone (UPy) group that can form Quadrupolar hydrogen bond;
The linear Poly-L-lactic acid that described both-end UPy modifies, dextrorotation poly(lactic acid) have following structure:
Wherein, n is 150 ~ 900;
The three arm star Poly-L-lactic acid that described three end UPy modify, dextrorotation poly(lactic acid) have following structure:
Wherein, n is 100 ~ 600.
Be provided for the method for the supramolecule stereoblock poly(lactic acid) preparing described easy Stereocomplex crystallization, specifically comprise the steps:
(1) UPy holds the preparation of functionalized PLLA and PDLA:
In Xi Dingke pipe, add hydroxy-end capped PLA and UPy-NCO, under 65 DEG C of conditions, vacuumize 1h, then carry out three gas displacements make Xi Dingke manage in final be argon atmosphere; Stannous octoate is added in Xi Dingke pipe, and the toluene of drying or DMF (DMF), stirring reaction 6 ~ 48h at 90 ~ 120 DEG C; Utilize Rotary Evaporators to remove organic solvent after reaction terminates, then the reaction product obtained is added in methylene dichloride or trichloromethane and dissolves, filter; At room temperature make solvent evaporates, the solid matter obtained is UPy and holds functionalized PLA, and namely UPy holds functionalized PLLA and PDLA; Then vacuum-drying 6h under 70 DEG C of conditions, for subsequent use;
Wherein, described PLA is linear PDLA, the PLLA of three arm stars or the PDLA of three arm stars of the linear PLLA of two-arm, two-arm;
The consumption of each reactant is: the mol ratio of hydroxy-end capped PLA and UPy-NCO is 1: 5 ~ 1: 30; The interpolation quality of reaction solvent toluene or DMF is 20 ~ 40 times that PLA adds quality; It is that PLA adds 0.4 ~ 10 ‰ of quality that stannous octoate adds quality;
(2) the blended preparation of PLLA/PDLA supramolecule Stereoblock polymers:
The UPy that step (1) prepares is held functionalized PLLA and PDLA, is dissolved in chloroform, make the concentration of polymers soln be 50g/L, and PLLA and PDLA mixing quality ratio is 1: 9 ~ 9: 1; After being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, at room temperature make solvent volatilize completely, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 70 DEG C, namely obtain the supramolecule stereoblock PLA of easy Stereocomplex crystallization;
Wherein, linear PLL A and the PDLA that UPy holds functionalized PLLA and PDLA to adopt both-end UPy functionalized, or three arm star PLLA and the PDLA that three end UPy are functionalized.
Compared with prior art, the invention has the beneficial effects as follows:
1, in the present invention using strong self-identifying can the forming Quadrupolar hydrogen bond interactional UPy group and prepare supramolecule stereoblock PLA as structural unit of linkage force.Compared with the PLLA/PDLA co-mixing system of similar mass, this supramolecule stereoblock PLA has higher Stereocomplex crystallizing power and degree of crystallinity, and crystallization velocity faster.Effectively improve the resistance toheat of PLA, also can improve its solvent resistance and hydrolytic resistance simultaneously;
2, PLA material prepared by the present invention carrys out authigenic material renewable resources, can degradablely be carbonic acid gas and water after using, environmental protection, and the pollution produced environment is little;
3, high molecular PLA stereoscopic composite material of the present invention adopts blending method preparation, and method is simple, and cost is low.
Accompanying drawing explanation
Fig. 1 is the DSC heating curve (10 DEG C/min) of the melting quench sample of embodiment 11 and comparative example 3.
Fig. 2 is embodiment 11 and the DSC heating curve of comparative example 3 sample under 140 DEG C of conditions after isothermal fusion-crystallization (10 DEG C/min).
The WAXD curve that Fig. 3 surveys after isothermal fusion-crystallization under 140 DEG C of conditions for embodiment 11 and comparative example 3 sample.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
The present invention prepare used reagent and medicine as follows: L-rac-Lactide and D-rac-Lactide purchased from Purao AS, recrystallization after acetic acid ethyl dissolution, for subsequent use; Octoate catalyst Ya Xi available from Sigma; 1,6 hexylene glycols are purchased from Tokyo HuaCheng Industry Co., Ltd; TriMethylolPropane(TMP) is purchased from Aladdin company.
The structural formula of UPy-NCO of the present invention is:
UPy-NCO is according to document (Sontjensetal.Macromolecules; 2008; 41:5703-5708) described method preparation; concrete steps are as follows: be added in 500ml there-necked flask by 2-amino-4-hydroxy-6-methylpyrimidine (10.0g); 0.5h is vacuumized at 65 DEG C; applying argon gas is protected; add 95.0g hexamethylene diisocyanate (HDI) and 3.2g methyl-2-pyrrolidone is catalyzer; wherein HDI mole number is 7 times of 2-amino-4-hydroxy-6-methylpyrimidine mole number, and catalyst content is 3% of total reactant quality.After reacting 16h at 100 DEG C, be dissolved in by product in trichloromethane, instillation volume ratio is (altogether 700ml) in the mixed solution of normal heptane and the isopropyl ether of 6: 1, precipitation, filtration.White solid product is placed in 50 DEG C of dry 10h of vacuum drying oven, for subsequent use.
Hydroxy-end capped linearly being made by oneself by the ring-opening polymerization of L-or D-rac-Lactide with three arm star PLLA, PDLA of three terminal hydroxy group end-blockings of the present invention's both-end used.Design molecular weight is that the concrete preparation process of three arm star PLLA of the three terminal hydroxy group end-blockings of 60kg/mol is as follows: will add in flask after 30gL-rac-Lactide, 0.067g TriMethylolPropane(TMP) and the drying of 0.09g stannous octoate; argon shield; under 130 DEG C of conditions, react 5h, obtain PLLA product.Dissolved in trichloromethane by the crude product obtained, the unreacted rac-Lactide of precipitation removing in dehydrated alcohol, filter, drying obtains polymkeric substance.By changing the mass ratio of initiator and rac-Lactide, prepare the polymkeric substance with different molecular weight.Molecular weight, the molecular weight distributing index (PDI) of polymkeric substance are measured by gel permeation chromatograph (GPC).Preparation condition and the molecular weight of three arm star PLLA, PDLA of the linear and three terminal hydroxy group end-blockings that both-end used herein is hydroxy-end capped list in table 1.
Table 1: the preparation condition of three arm star PLLA, PDLA of the linear and three terminal hydroxy group end-blockings that both-end is hydroxy-end capped and molecular weight
In polymer name, 2L, 2D, 3L, 3D represent three arm star PLLA, PDLA of the hydroxy-end capped linear PLL A of both-end, PDLA and three terminal hydroxy group end-blockings respectively, the weight-average molecular weight of suffix numeral polymkeric substance.
Molecular weight is tested: molecular weight of copolymer distribution adopts Waters gel permeation chromatograph to measure, and probe temperature is 30 DEG C, and moving phase is tetrahydrofuran (THF), and standard model is monodisperse polystyrene.
1) UPy holds the preparation of functionalized PLLA and PDLA
In embodiment 1 ~ 8 below, by linear and three arm star PLLA of three terminal hydroxy group end-blockings, the reaction of PDLA and UPy-NCO that both-end is hydroxy-end capped, prepare three linear functionalized with three end UPy arm star PLLA, PDLA that both-end UPy is functionalized, specific as follows:
Add hydroxy-end capped PLA, UPy-NCO in Xi Dingke pipe after, under 65 DEG C of conditions, vacuumize 1h.Carry out three gas displacements to make to be finally argon atmosphere in Xi Dingke pipe; Stannous octoate is added in Xi Dingke pipe, and the toluene of drying or DMF, stirring reaction 6 ~ 48h at 90 ~ 120 DEG C; Utilize Rotary Evaporators to remove organic solvent after reaction terminates, be then added in methylene dichloride and dissolve, filter.At room temperature make solvent evaporates, the solid matter obtained is UPy and holds functionalized PLA.Under 70 DEG C of conditions, vacuum-drying 6h, for subsequent use.Wherein, the mol ratio of PLA and UPy-NCO is 1: 5 ~ 1: 30.The interpolation quality of toluene or DMF is 20 ~ 40 times of PLA quality, and it is 0.4 ~ 10 ‰ of PLA quality that stannous octoate adds quality.
Utilize
1hNMR determines the terminal hydroxy group reactivity of PLA.Probe temperature is room temperature, and solvent is deuterochloroform, and chemical shift is corrected by solvent peak.Represent the proton resonance peak of the methyne in PLA end lactic acid units at the chemical shift resonance peak that is 0.43ppm place, represent the proton resonance peak of amido in UPy at the chemical shift resonance peak that is 13.1ppm place.Be benchmark according to the area at the methine protons peak of lactic acid units in PLA main chain, the terminal hydroxy group reactivity of PLA can be obtained.
Table 2:UPy holds the preparation of functionalized linear, three arm star PLLA and PDLA
In polymer name, 2L-U, 2D-U, 3L-U, 3D-U represent linear PLL A, the PDLA of both-end UPy end-blocking and three arm star PLLA, PDLA of three end UPy end-blockings respectively, the weight-average molecular weight of suffix numeral polymkeric substance.
As shown in Table 2, hold in functionalized PLLA and PDLA at preparation UPy, when being 16h when reacted, the terminal hydroxy group reactivity of PLA is higher, is greater than 85%.
2) the blended preparation of supramolecule stereoblock PLA
Embodiment 9 ~ 13
Hold functionalized PLLA and PDLA to be dissolved in chloroform the UPy of certain mass ratio, the concentration making polymers soln is 50g/L, after being uniformly mixed, being watered by polymers soln and casts from tetrafluoroethylene culture dish; At room temperature make solvent volatilize completely, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 70 DEG C, namely obtain the supramolecule stereoblock PLA of easy Stereocomplex crystallization.
Comparative example 1 ~ 5
PLLA and PDLA functionalized for the hydroxyl terminal of certain mass ratio is dissolved in chloroform, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then make solvent volatilize completely under room temperature, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C.
The test of crystallization behavior: use DSC test, nitrogen atmosphere.In the test of non-isothermal cold crystallization, sample from room temperature to 250 DEG C with 50 DEG C/min, keeps 2min to eliminate thermal history, is then cooled to 0 DEG C with 100 DEG C/min, after keeping 3min, then is warming up to 250 DEG C with 10 DEG C/min at 0 DEG C.In isothermal melting crystallization test, sample with 50 DEG C/min from room temperature to 250 DEG C, keep 2min to eliminate thermal history, then with 100 DEG C/min fast cooling extremely set probe temperature, keep for some time to make the complete crystallization of polymkeric substance, then be warming up to 250 DEG C of its melting behaviors of detection with 10 DEG C/min.
Kinetics of crystallization and Thermal Parameter calculate: in the 10 DEG C/min temperature-rise period after non-isothermal cold crystallization, the endotherm(ic)peak between 140 DEG C to 180 DEG C is the melting peak of PLLA, PDLA homogeneity crystallization, and peak temperature is homogeneity crystalline melt point (T
m, hc), integral area is homogeneity crystallization melting enthalpy (Δ H
m, hc).Endotherm(ic)peak between 180 to 240 DEG C is the melting peak of PLLA/PDLA blend Stereocomplex crystallization, and peak temperature is Stereocomplex crystalline melt point (T
m, sc), integral area is Stereocomplex crystallization enthalpy (Δ H
m, sc).Relative fractions (the f of Stereocomplex crystallization
sc) by formula f
sc=Δ H
m, sc/ (Δ H
m, sc+ Δ H
m, hc) calculate.Based on the data of isothermal melting crystallization, flexible chain (t
0.5) obtained by Avrami Equation for Calculating, concrete grammar reference literature ACSAppliedMaterials & Interfaces, 2009, Isosorbide-5-Nitrae 02.Wherein, hc represents homogeneity crystallization, and sc represents Stereocomplex crystallization.
Wide-angle X ray diffractor (WAXD) is utilized to analyze crystalline texture and the crystal formation of blend.Non-UPy is modified supramolecule Stereoblock polymers that PLLA/PDLA blend and UPy modify in thermocompressor at 250 DEG C melting 2min eliminate thermal history, be pressed into certain thickness thin slice, then isothermal crystal certain hour in fast transfer to 140 DEG C baking oven, make it complete crystallization, and the thin slice after crystallization is carried out WAXD analysis.
The Thermal Parameter of melting quench sample in non-isothermal cold crystallization and melting process of embodiment 9 ~ 13 and comparative example 1 ~ 5 is as shown in table 3, and wherein temperature rise rate is 10 DEG C/min.
Table 3: the Thermal Parameter of melting quench sample in non-isothermal cold crystallization and melting process of embodiment 9 ~ 13 and comparative example 1 ~ 5
From table 3 and Fig. 1: for etc. blended hydroxy-end capped PLLA and the PDLA system of mass ratio, melting enthalpy and the relative content thereof of its Stereocomplex crystallization are less, and the main homogeneity crystallization forming low melting point in co-mixing system is described.When the weight-average molecular weight of PLLA and PDLA is greater than 85kg/mol, its Stereocomplex crystallization relative content is less than 20%.For the supramolecule Stereoblock polymers be made up of the linear of UPy end-blocking and three arm star equivalent PLLA, PDLA, the dystectic Stereocomplex crystallization of main formation in temperature-rise period.Although the melting peak of homogeneity crystallization and Stereocomplex crystallization appears in embodiment 9,11 sample at temperature-rise period simultaneously, compared with comparative example 1,3, the content of its Stereocomplex crystallization enlarges markedly.Comparing embodiment 9,10 known, the supramolecule Stereoblock polymers that more three arm star PLLA and PDLA of UPy group content form more easily forms Stereocomplex crystallization.Comparing embodiment 12,13 and comparative example 4,5 known, for the non-PLLA/PDLA system waiting mass ratio, construct by UPy group crystallization velocity and the Stereocomplex crystalline content that supramolecule Stereoblock polymers also effectively can improve material.
Table 4: kinetics in 140 DEG C of isothermal melting crystallizations and temperature-rise period of embodiment 9 ~ 11 and comparative example 1 ~ 3 sample and Thermal Parameter
From table 4 and Fig. 2,3, the supramolecule Stereoblock polymers containing UPy group is main in isothermal melting crystallisation process forms dystectic Stereocomplex crystallization.For the PLLA/PDLA co-mixing system that terminal hydroxy group is modified, in isothermal melting crystallization, form homogeneity crystallization and Stereocomplex crystallization, and homogeneity crystallization is dominant simultaneously.In addition, the t of the supramolecule Stereoblock polymers of UPy group is contained in embodiment 9 ~ 11
0.5significantly lower than comparative example 1 ~ 3 sample.The result of these non-isothermals and isothermal crystal demonstrates and significantly improves the Stereocomplex crystallizing power of PLA and the content of Stereocomplex crystallization by Quadrupolar hydrogen bond strong between the UPy group PLLA/PDLA supramolecule Stereoblock polymers formed that interacts, and also improves its crystallization velocity simultaneously.
For confirming to be conducive to forming Stereocomplex crystallization containing the PLLA/PDLA supramolecule Stereoblock polymers of UPy group in the present invention further, WAXD test is carried out to 140 DEG C of isothermal melting crystallized sample of example 11 and comparative example 3.As shown in Figure 3: embodiment 11 only presents the diffraction peak of Stereocomplex crystallization, and occurs the homogeneity crystallization of PLA and the diffraction peak of Stereocomplex crystallization in comparative example 3 simultaneously, and the diffraction peak of homogeneity crystallization is stronger.In Fig. 3, sc represents Stereocomplex crystallization, and hc represents homogeneity crystallization.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, a lot of distortion can also be had.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (2)
1. the supramolecule stereoblock poly(lactic acid) of easily Stereocomplex crystallization, be made up of elementary cell, it is characterized in that, described elementary cell is functionalized linear Poly-L-lactic acid, the dextrorotation poly(lactic acid) of both-end, or functionalized three arm star Poly-L-lactic acid, the dextrorotation poly(lactic acid) of three ends, and the end group of elementary cell is 2-urea groups-4 [1H]-pyrimidone group that can form Quadrupolar hydrogen bond;
The linear Poly-L-lactic acid that described both-end UPy modifies, dextrorotation poly(lactic acid) have following structure:
Wherein, n is 150 ~ 900;
The three arm star Poly-L-lactic acid that described three end UPy modify, dextrorotation poly(lactic acid) have following structure:
Wherein, n is 100 ~ 600.
2., for the preparation of the method for the supramolecule stereoblock poly(lactic acid) of Stereocomplex crystallization easy described in claim 1, it is characterized in that, specifically comprise the steps:
(1) UPy holds the preparation of functionalized PLLA and PDLA:
In Xi Dingke pipe, add hydroxy-end capped PLA and UPy-NCO, under 65 DEG C of conditions, vacuumize 1h, then carry out three gas displacements make Xi Dingke manage in final be argon atmosphere; Stannous octoate is added in Xi Dingke pipe, and the toluene of drying or DMF, stirring reaction 6 ~ 48h at 90 ~ 120 DEG C; Utilize Rotary Evaporators to remove organic solvent after reaction terminates, then the reaction product obtained is added in methylene dichloride or trichloromethane and dissolves, filter; At room temperature make solvent evaporates, the solid matter obtained is UPy and holds functionalized PLA, and namely UPy holds functionalized PLLA and PDLA; Then vacuum-drying 6h under 70 DEG C of conditions, for subsequent use;
Wherein, described PLA is linear PDLA, the PLLA of three arm stars or the PDLA of three arm stars of the linear PLLA of two-arm, two-arm;
The consumption of each reactant is: the mol ratio of hydroxy-end capped PLA and UPy-NCO is 1: 5 ~ 1: 30; The interpolation quality of reaction solvent toluene or DMF is 20 ~ 40 times that PLA adds quality; It is that PLA adds 0.4 ~ 10 ‰ of quality that stannous octoate adds quality;
(2) the blended preparation of PLLA/PDLA supramolecule Stereoblock polymers:
The UPy that step (1) prepares is held functionalized PLLA and PDLA, is dissolved in chloroform, make the concentration of polymers soln be 50g/L, and PLLA and PDLA mixing quality ratio is 1: 9 ~ 9: 1; After being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, at room temperature make solvent volatilize completely, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 70 DEG C, namely obtain the supramolecule stereoblock PLA of easy Stereocomplex crystallization;
Wherein, linear PLL A and the PDLA that UPy holds functionalized PLLA and PDLA to adopt both-end UPy functionalized, or three arm star PLLA and the PDLA that three end UPy are functionalized.
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| CN113527643A (en) * | 2021-07-30 | 2021-10-22 | 广东海洋大学 | Polylactic acid and stereocomplex film material thereof and preparation method |
| CN115594834A (en) * | 2021-07-07 | 2023-01-13 | 重庆大学（Cn） | Application of ureidopyrimidone telechelic polylactic acid supramolecular polymer as plasticizer and polymer material prepared from ureidopyrimidone telechelic polylactic acid supramolecular polymer |
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| CN106700098A (en) * | 2016-12-15 | 2017-05-24 | 浙江大学 | Preparation method of biodegradable supermolecule polylactic acid microspheres |
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| CN113004507A (en) * | 2021-03-08 | 2021-06-22 | 中国科学院长春应用化学研究所 | Rapidly-crystallized poly-L-lactic acid and preparation method thereof, and polylactic acid foam material and preparation method thereof |
| CN113004507B (en) * | 2021-03-08 | 2022-12-20 | 中国科学院长春应用化学研究所 | Rapidly-crystallized poly-L-lactic acid and preparation method thereof, and polylactic acid foam material and preparation method thereof |
| CN115594834A (en) * | 2021-07-07 | 2023-01-13 | 重庆大学（Cn） | Application of ureidopyrimidone telechelic polylactic acid supramolecular polymer as plasticizer and polymer material prepared from ureidopyrimidone telechelic polylactic acid supramolecular polymer |
| CN115594958A (en) * | 2021-07-07 | 2023-01-13 | 重庆大学（Cn） | Polymer material capable of being processed at low temperature and preparation method thereof |
| CN115594834B (en) * | 2021-07-07 | 2023-06-30 | 重庆大学 | Application of ureido pyrimidinone telechelic polylactic acid supermolecular polymer as plasticizer and polymer material prepared by using same |
| CN115594958B (en) * | 2021-07-07 | 2023-11-17 | 重庆大学 | Polymer material capable of being processed at low temperature and preparation method thereof |
| CN113527643A (en) * | 2021-07-30 | 2021-10-22 | 广东海洋大学 | Polylactic acid and stereocomplex film material thereof and preparation method |
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