CN104262917A - Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly - Google Patents
Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly Download PDFInfo
- Publication number
- CN104262917A CN104262917A CN201410475711.4A CN201410475711A CN104262917A CN 104262917 A CN104262917 A CN 104262917A CN 201410475711 A CN201410475711 A CN 201410475711A CN 104262917 A CN104262917 A CN 104262917A
- Authority
- CN
- China
- Prior art keywords
- molecular
- poly
- lactic acid
- weighpolylactic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 C=C(*c1ccccc1)O*OC(*c1ccccc1)=* Chemical compound C=C(*c1ccccc1)O*OC(*c1ccccc1)=* 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of modification of biological high-molecular materials, and aims to provide a preparation method of a high-molecular PLA three-dimensional composite material capable of being crystallized rapidly. The high-molecular PLA three-dimensional composite material capable of being crystallized rapidly can be prepared by solution or melt blending of a PLA matrix and an organic metal phosphonate nucleating agent. According to the invention, three-dimensional composite crystallization of a high-molecular PLLA/PDLA (Poly L Lactic Acid/Poly-D-Lactic Acid) blend is promoted by adopting organic metal phosphonate; the homogeneous crystallization is inhibited; the three-dimensional composite crystallization speed and the crystallization degree of the blend are greatly increased; the three-dimensional composite crystallization degree can be above 40%; the processibility, the heat-resistant property and the mechanical property of the PLLA/PDLA blend are increased effectively; simultaneously, the solvent resistance and the degradation resistance of PLA are also improved.
Description
Technical field
The invention relates to bio-based field of high polymer material modification, particularly can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization.
Background technology
Poly(lactic acid) (PLA) is the degradable biological based high molecular material of a quasi-representative, there are good biological degradability, biocompatibility, workability, mechanical property etc., be widely used in the fields such as biomedical engineering, wrapping material, Phthalates, textile fibres, film.But as hemicrystalline thermoplastic polyester, the crystallization rate of PLA is comparatively slow, degree of crystallinity is low, and this has a strong impact on its workability and thermotolerance, constrains the application of PLA at industrial circle.Stereoregulated PLA has two kinds of optically active isomers, i.e. Poly-L-lactic acid (PLLA) and dextrorotation poly(lactic acid) (PDLA).When PLLA and PDLA is blended, stereo complex crystallization can be formed, its fusing point up to 230 DEG C, than the homogeneity crystallization height about 50 DEG C of independent PLLA or PDLA.The over-all properties of PLA stereo complex crystalline material is similar to the engineering plastics such as PET, nylon; Compared with homogeneity crystalline material, three-dimensional compound crystalline material has higher intensity, modulus and excellent solvent resistant, resistant to hydrolysis performance, so three-dimensional composite junction crystallization improves the effective way of the over-all propertieies such as PLA thermotolerance, the speed and the degree of crystallinity that how effectively to improve the three-dimensional composite junction crystallization of PLA are significant to the industrial application widening bio-based PLA.
But in PLLA/PDLA co-mixing system, there is the competition of homojunction crystallization and three-dimensional composite junction crystallization, when PLLA and PDLA molecular weight is larger (weight-average molecular weight >40kg/mol), dystectic three-dimensional compound crystal is difficult to be formed, and mainly forming the homogeneity crystallization of low melting point, this becomes bottleneck prepared by high heat-resisting PLA stereo complex material.So one of gordian technique in high heat-resisting PLA stereo complex material preparation how optionally to promote its three-dimensional composite junction crystallization, suppresses its homojunction crystallization, and how to improve the speed of three-dimensional compound crystal.Interpolation nucleator is industrial conventional acceleration crystallization, improves the method for degree of crystallinity and adjustment crystal formation.Nucleator plays the effect of heterogeneous nucleation in polymer crystallization process, the crystalizing interface free energy of semi-crystalline polymer can be reduced, polymer molecular chain can be made to be adsorbed on its surface and to form nucleus, the nucleation density of polymkeric substance can be improved, thus improve crystallization rate and the degree of crystallinity of polymkeric substance.In addition, to grow nonparasitically upon another plant the mechanism of crystallization based on nucleator surface, usual nucleator crystal in one direction with polymer lattice structure matching, thus the crystalline structure adding also controllable polymkeric substance of nucleator.
Organo-metallic phosphonate is the nucleator that a class is commonly used, patent (as international monopoly WO 2005/097894A1, Chinese patent CN 101423625B) and paper (Pan etc., ACS Appl.Mater.Interfaces, 2009,1,402-411) report that organo-metallic phosphonate can promote the homojunction crystallization of PLLA, significantly improve speed and the degree of crystallinity of homogeneity crystallization, but the fusing point adopting material prepared in this way only has 160 ~ 170 DEG C, heat-drawn wire is usually less than 110 DEG C, can not meet the needs of high heat-resisting occasion.The crystalline structure of the three-dimensional compound crystal of homogeneity crystallization (as alpha-crystal form) and PLLA/PDLA due to PLLA or PDLA is completely different, thus the nucleator of PLLA homogeneity crystallization usually to the three-dimensional compound crystal of PLLA/PDLA without obvious nucleating effect.For PLLA/PDLA co-mixing system, US Patent No. 2008/0097074A1 reports that aromatic series carbamide compounds optionally promotes the three-dimensional compound crystal between PLLA and PDLA; Urayama etc. (Polymer, 2003,44,5635 – 5641) report that the phosphonic acid ester complex compound of aluminium can accelerate the three-dimensional composite junction crystallization of PLLA/PDLA blend.But these nucleation-accelerant chemical structures are complicated, and more difficult synthesis, preparation cost is higher, affects its large-scale application.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provide a kind of and prepare that three-dimensional composite junction crystallization rate is fast, degree of crystallinity is high, easy processing, the high molecular that production cost is low, high heat-proof polylactic acid stereo complex material method.For solving the problems of the technologies described above, solution of the present invention is:
Thering is provided can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, comprise the use of organic metal phosphonic acid salt nucleator, concrete preparation process comprises: get poly(lactic acid) matrix, organo-metallic phosphonate nucleator adopts solution or melt blending, and can obtain can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization;
Wherein, the quality of organo-metallic phosphonate nucleator accounts for 0.1% ~ 3% of total composition, and the quality of poly(lactic acid) matrix accounts for 99.9 ~ 97% of total composition, and the mass percent sum of each component is 100%; Described poly(lactic acid) matrix refers to Poly-L-lactic acid (PLLA) and dextrorotation poly(lactic acid) (PDLA), and in poly(lactic acid) matrix, the mass percent of Poly-L-lactic acid is 50% ~ 90%, and the mass percent of dextrorotation poly(lactic acid) is 10% ~ 50%;
Described organo-metallic phosphonate nucleator adopts any one material in phenide phosphonate, phenide phosphinates or phenylbenzene metal phosphinate hydrochlorate.
In the present invention, when adopting solution blended process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator, be dissolved in easy volatile solvent, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then easy volatile solvent is made to volatilize completely under room temperature, tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization again.
In the present invention, described easy volatile solvent adopts methylene dichloride or chloroform.
In the present invention, when adopting melt-blending process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator add in forcing machine (single screw extrusion machine or twin screw extruder), then mixing 3min at 230 DEG C, extrude pelletizing again, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization.
In the present invention, when adopting melt-blending process to prepare, in forcing machine, also carbodiimide hydrolysis-resisting agent, Hinered phenols antioxidant can be added.
In the present invention, the phosphatic structural formula of described phenide is:
Wherein, M is divalent metal.
In the present invention, the structural formula of described phenide phosphinates is:
Wherein, M is divalent metal.
In the present invention, the structural formula of described phenylbenzene metal phosphinate hydrochlorate is:
Wherein, M is divalent metal.
In the present invention, described M adopts at least one divalent metal (preferred zinc) in zinc, barium, calcium.
In the present invention, the weight-average molecular weight of described Poly-L-lactic acid, dextrorotation poly(lactic acid) is all greater than 80kg/mol, and optical purity is greater than 95%; The particle diameter of organo-metallic phosphonate nucleator is between 10 ~ 30 microns.
In the present invention, the concrete preparation process of PDLA is as follows: will add in flask after 50g D-rac-Lactide, 0.08g lauryl alcohol and the drying of 0.05g stannous octoate, argon shield, reacts 5h, obtain polymeric articles at 130 DEG C.
In the present invention, the preparation method of phenyl-phosphonic acid zinc (PPZn), phenyl-phosphonic acid calcium (PPCa) and phenyl-phosphonic acid barium (PPBa) is as follows: be dissolved in by 100g phenyl-phosphonic acid in 2.0L deionized water, then add the ZnCl of equimolar amount
2, CaCl
2or BaCl
2, stir, between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.
In the present invention, diphenyl phosphonic acid zinc (DPPZn) preparation method is as follows: be dissolved in 100mL deionized water by 10g diphenyl phosphonic acid, adds the ZnCl of its 1/2nd molar weight
2, with between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.Wherein, if by ZnCl
2replace to CaCl
2or BaCl
2, DPPCa and DPPBa can be prepared respectively.
In the present invention, phenyl phosphinic acid zinc (PP3Zn) preparation method is as follows: be dissolved in 100mL deionized water by 10g phenyl phosphinic acid, adds the ZnCl of its 1/2nd molar weight
2, with between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.Wherein, if by ZnCl
2replace to CaCl
2or BaCl
2, PP3Ca and PP3Ba can be prepared respectively.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention adopts organo-metallic phosphonate to promote the three-dimensional composite junction crystallization of high molecular PLLA/PDLA blend, inhibit its homojunction crystallization, make the three-dimensional compound crystal speed of blend, degree of crystallinity significantly promotes, the degree of crystallinity of its three-dimensional compound crystal can reach more than 40%, effectively improve the workability of PLLA/PDLA blend, resistance toheat and mechanical property, also can improve solvent resistance and the degradation resistance of PLA simultaneously;
2, the crystallization nucleating agent in the present invention is organo-metallic phosphonate, and particle diameter, between 10 ~ 30 microns, has good consistency with PLA matrix, easily dispersed in the base, improves nucleating effect;
3, in the present invention, organo-metallic phosphonates compound can adopt replacement(metathesis)reaction one step to prepare, and Heat stability is good can adopt melting or solution method to mix with polymeric matrix, and technique is simple, and cost is low, can realize large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is embodiment 1-4, embodiment 6 and the comparative example 1 DSC curve in 10 DEG C/min temperature-fall period.
Fig. 2 is the DSC curve that embodiment 1-4, embodiment 6 and comparative example 1 are lowered the temperature in rear 10 DEG C/min temperature-rise period at 10 DEG C/min.
Fig. 3 is the DSC curve of embodiment 10 in 10 DEG C/min cooling and 10 DEG C/min temperature-rise period afterwards.
Fig. 4 is embodiment 1,10 and the isothermal melting crystallization DSC curve of comparative example 1 under 140 DEG C of conditions.
The WAXD curve that Fig. 5 surveys after isothermal fusion-crystallization under 140 DEG C of conditions for embodiment 1 and comparative example 1.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
Can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, by adding organo-metallic phosphonate nucleator in high molecular PLLA/PDLA co-mixing system, optionally facilitate the three-dimensional composite junction crystallization of PLLA/PDLA, improve speed and the degree of crystallinity of its three-dimensional compound crystal, improve material thermal resistance, adopt the method only to add the nucleator of about 1wt%, the heat-proof polylactic acid material that three-dimensional compound crystal content is high can be obtained.
Can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, concrete preparation process comprises: get PLLA, PDLA, organo-metallic phosphonate nucleator, adopt solution or melt blending, can obtain can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization; Wherein, the quality of organo-metallic phosphonate nucleator accounts for 0.1% ~ 3% of total composition, and the quality of poly(lactic acid) matrix accounts for 99.9 ~ 97% of total composition, and the mass percent sum of each component is 100%; In poly(lactic acid) matrix, the mass percent of PLLA is the mass percent of 50% ~ 90%, PDLA is 10% ~ 50%.In the present invention, the solution of PLLA, PDLA and crystallization nucleating agent, melt-mixing method are not particularly limited, and known method can be adopted to carry out.
When adopting solution blended process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator, be dissolved in the easy volatile such as methylene dichloride or chloroform solvent, polymer solution concentration is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then easy volatile solvent is made to volatilize completely under room temperature, tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization again.
When adopting melt-blending process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator add in forcing machine (single screw extrusion machine or twin screw extruder), then mixing 3min at 230 DEG C, extrude pelletizing again, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization.Wherein, also carbodiimide hydrolysis-resisting agent, Hinered phenols antioxidant can be added in forcing machine.
The weight-average molecular weight of described Poly-L-lactic acid, dextrorotation poly(lactic acid) is all greater than 80kg/mol, and optical purity is greater than 95%.
Described organo-metallic phosphonate nucleator adopts any one material in phenide phosphonate, phenide phosphinates or phenylbenzene metal phosphinate hydrochlorate, and the particle diameter of organo-metallic phosphonate nucleator is between 10 ~ 30 microns.
The phosphatic structural formula of phenide is:
Wherein, M is divalent metal, comprises one or more in zinc, barium, calcium etc., preferably finds the best results of zinc salt further.
The structural formula of phenide phosphinates is:
Wherein, M is divalent metal, comprises one or more in zinc, barium, calcium etc., preferably finds the best results of zinc salt further.
The structural formula of phenylbenzene metal phosphinate hydrochlorate is:
Wherein, M is divalent metal, comprises one or more in zinc, barium, calcium etc., preferably finds the best results of zinc salt further.
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.
In the embodiment of the present invention, PLLA used is produced by Japanese Shimazu company, and its number-average molecular weight is 116kg/mol, and weight-average molecular weight is 198kg/mol.
PDLA used is made by oneself by the ring-opening polymerization of D-rac-Lactide, and its number-average molecular weight is 190kg/mol, and weight-average molecular weight is 298kg/mol.Concrete preparation process is as follows: will add in flask after 50g D-rac-Lactide (purchased from Purao AS), 0.08g lauryl alcohol (purchased from Amethyst Chemical company) and the drying of 0.05g stannous octoate; argon shield; at 130 DEG C, react 5h, obtain polymeric articles.
Carbodiimide hydrolysis-resisting agent (model TMP-2000) and Hinered phenols thermo-stabilizer are provided by Hangzhou Xi Mao novel material Science and Technology Ltd..
Nucleator phenyl-phosphonic acid zinc (PPZn), nucleator phenyl-phosphonic acid calcium (PPCa) and phenyl-phosphonic acid barium (PPBa) reference (ACS Appl.Mater.Interfaces 2009,1,402-411) prepare, concrete grammar is as follows: be dissolved in 2.0L deionized water by 100g phenyl-phosphonic acid (purchased from Qingdao Fu Silin Chemical Industry Science Co., Ltd), then add the ZnCl of equimolar amount
2, CaCl
2or BaCl
2, stir, between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.
Diphenyl phosphonic acid zinc (DPPZn) preparation method is as follows: be dissolved in 100mL deionized water by 10g diphenyl phosphonic acid (purchased from TCI), add the ZnCl of its 1/2nd molar weight
2, with between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.
Phenyl phosphinic acid zinc (PP3Zn) preparation method is as follows: be dissolved in 100mL deionized water by 10g phenyl phosphinic acid (purchased from TCI), add the ZnCl of its 1/2nd molar weight
2, with between 5M NaOH aqueous solution adjust ph to 5 ~ 6, filter, drying obtains product.
Embodiment 1 ~ 7 adopts the blended preparation of solution method
Polylactic acid based weight per-cent is 99%, and different sorts nucleator mass percent is 1%.PLLA, PDLA and nucleator being formed after quality proportioning takes by table 1 is respectively dissolved in chloroform, polymer solution concentration is 50g/L, stirs and makes it to mix, then water and cast from tetrafluoroethylene culture dish, under room temperature, solvent is volatilized completely, then dry 6h in 60 DEG C of vacuum drying ovens.Wherein, if chloroform is replaced to methylene dichloride, the preparation of the present embodiment also can be completed.
Embodiment 8 adopts melt mixing to prepare
Polylactic acid based weight per-cent is 99%, and nucleator mass percent is 1%.Forming quality proportioning by table 1 will add in HAAKE MiniLab II double-screw mixer after 49.5 mass parts PLLA, 49.5 mass parts PDLA, 1 mass parts PPZn pre-mixing evenly, mixing 3min at 230 DEG C, then extrudes pelletizing.
In order to further illustrate in PLLA, PDLA equivalent co-mixing system, the nucleating effect of nucleator, in comparative example 1, only adopts solution method blended PLLA, PDLA of equivalent.Form quality proportioning by table 1 and take the PLLA of 50 mass parts and the PDLA of 50 mass parts respectively, in solution chloroform, polymer solution concentration is 50g/L, stirring makes it to mix, then water and cast from tetrafluoroethylene culture dish, under room temperature, solvent is volatilized completely, then dry 6h in 60 DEG C of vacuum drying ovens.
The test of crystallization behavior: use DSC test, nitrogen atmosphere.In non-isothermal melting behavior crystallization test, 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 10 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 from room temperature to 250 DEG C, keeps 2min to eliminate thermal history with 50 DEG C/min, then with 100 DEG C/min fast cooling to 140 DEG C, keeps 60min to make the complete crystallization of polymkeric substance, then is warming up to 250 DEG C with 10 DEG C/min.
Kinetics of crystallization and Thermal Parameter calculate: in 10 DEG C/min temperature-fall period, and the peak temperature of crystalline exotherm peak is melt crystallization temperature (T
mc), integration gained area is fusion-crystallization enthalpy (△ H
mc).In 10 DEG C/min temperature-rise period after non-isothermal melting behavior crystallization or isothermal crystal, the peak temperature of cold crystallization exothermic peak is cold crystallization temperature (T
cc), integral area is cold crystallization enthalpy (△ H
cc); Endotherm(ic)peak between 160 DEG C to 190 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 (△ H
m, hc).Between 190 DEG C to 250 DEG C, endotherm(ic)peak is the melting peak of the three-dimensional compound crystal of PLLA/PDLA blend, and peak temperature is three-dimensional compound crystal fusing point (T
m, sc), integral area is three-dimensional compound crystal enthalpy (△ H
m, sc).Relative fractions (the f of three-dimensional compound crystal
sc) by formula f
sc=△ H
m, sc/ (△ H
m, sc+ △ H
m, hc) calculate.Based on the data of isothermal crystal, flexible chain (t0.5) is obtained by Avrami Equation for Calculating, concrete grammar reference literature ACS Applied Materials & Interfaces, 2009, Isosorbide-5-Nitrae 02-411.
Wide-angle X ray diffractor (WAXD) is utilized to analyze crystalline texture and the crystal formation of blend.By the PLLA/PDLA blend added and do not add nucleator in thermocompressor at 250 DEG C melting 2min eliminate thermal history, be pressed into certain thickness thin slice, then isothermal crystal 1h in fast transfer to 140 DEG C baking oven, makes it complete crystallization, and the thin slice after crystallization is carried out WAXD analysis.
Polarizing microscope (POM) is utilized to observe spherocrystal density.To add and not add PLLA/PDLA blend melting 2min, then fast cooling to 140 DEG C in 250 DEG C of thermal station of nucleator, place 1h and make it complete crystallization, after crystallization, utilize POM to observe its spherocrystal pattern.
Utilize dynamic properties tester analysis of material storage modulus at different temperatures.By adding and do not add PLLA/PDLA blend isothermal fusion-crystallization under 140 DEG C of conditions of nucleator, be then cut into 15 × 6 × 0.5mm
3thin slice, carry out dynamic properties test.
Table 1: the Thermal Parameter in different nucleater modified PLLA/PDLA and the crystallization of unmodified PLLA/PDLA blend non-isothermal melting behavior
As shown in Table 1: compared with blended with unmodified PLLA/PDLA (comparative example 1), after adding organic metal phosphonic acid salt nucleator, crystallization velocity is accelerated, can crystallization completely in 10 DEG C/min temperature-fall period, in temperature-rise period afterwards, do not occur cold crystallization, three-dimensional compound crystal content improves (Fig. 1, Fig. 2) simultaneously.Preferred discovery PPZn (embodiment 1) best results, is fully formed the three-dimensional compound crystal of high-melting-point after adding 1wt%.Embodiment 1 and embodiment 8 are compared discovery, and blend method does not make significant difference to crystallization behavior, adopts solution blending substantially identical with the modification PLLA/PDLA blend Thermal Parameter of melt blending.
Embodiment 9 ~ 11
PLLA, PDLA equivalent is blended, nucleator PPZn consumption is different, PLLA, PDLA and nucleator being formed after quality proportioning takes by table 2 is respectively dissolved in chloroform, polymer solution concentration is 50g/L, stirring makes it to mix, then water and cast from tetrafluoroethylene culture dish, under room temperature, solvent is volatilized completely, then dry 6h in 60 DEG C of vacuum drying ovens.DSC is utilized to test (testing method is the same, Fig. 3) non-isothermal melting behavior crystallization behavior.During different nucleator consumption, the Thermal Parameter of PLLA/PDLA blending and modifying material is as table 2.
Table 2: Thermal Parameter during different nucleator consumption in the crystallization of PLLA/PDLA blend non-isothermal melting behavior
From table 2 and Fig. 3: along with nucleator consumption increases, the three-dimensional compound crystal speed of PLLA/PDLA co-mixing system is accelerated, and three-dimensional compound crystal content improves, and as PPZn nucleator consumption >=1wt%, can be fully formed three-dimensional compound crystal.
Embodiment 12,13
The content of PLLA, PDLA is different, all containing 1wt%PPZn nucleator; PLLA, PDLA and nucleator being formed after quality proportioning takes by table 3 is respectively dissolved in chloroform, polymer solution concentration is 50g/L, stirs and makes it to mix, then water and cast from tetrafluoroethylene culture dish, under room temperature, solvent is volatilized completely, then dry 6h in 60 DEG C of vacuum drying ovens.DSC is utilized to test (testing method is the same) non-isothermal melting behavior crystallization behavior.During different PLLA, PDLA content, the Thermal Parameter of PLLA/PDLA/PPZn blend is as table 3.
For further illustrating the nucleogenesis of nucleator to non-equivalent PLLA/PDLA co-mixing system, all not containing nucleator in comparative example 12, comparative example 13, and the quality proportioning of PLLA, PDLA is with embodiment 12,13, PLLA, PDLA being formed after quality proportioning takes by table 3 is respectively dissolved in chloroform, polymer solution concentration is 50g/L, stirs and makes it to mix, then water and cast from tetrafluoroethylene culture dish, under room temperature, solvent is volatilized completely, then dry 6h in 60 DEG C of vacuum drying ovens.DSC is utilized to test (testing method is the same) non-isothermal melting behavior crystallization behavior.During different PLLA, PDLA content, the Thermal Parameter of PLLA/PDLA blend is as table 3.
The Thermal Parameter of the PLLA/PDLA blend nonisothermal crystallization of different PLLA, PDLA content of table 3
As shown in Table 3: for the PLLA/PDLA co-mixing system of the mass ratio such as PLLA, PDLA be non-, the crystallization velocity of co-mixing system can be improved after adding organic metal phosphonic acid salt nucleator equally, improve three-dimensional compound crystal content.In conjunction with the embodiments 1,12,13 and comparative example 1,12,13 can find, when the mass percent of PLLA/PDLA is between 50/50 to 70/30, after adding 1wt%PPZn nucleator, all can be fully formed three-dimensional compound crystal.When the mass percent of PLLA/PDLA is 70/30, after adding 1wt%PPZn nucleator, can be fully formed three-dimensional compound crystal, the visible content adopting this technology can reduce PDLA in co-mixing system, reduces the manufacturing cost of high patience PLA material.
The isothermal melting kinetics of crystallization under 140 DEG C of conditions (testing method as above, Fig. 4) by dsc analysis comparative example 1 and embodiment 1,9,10 blend, kinetics and Thermal Parameter are as table 4.
Table 4 before modified after PLLA/PDLA blend 140 DEG C time the kinetics of isothermal melting crystallization and Thermal Parameter
From table 4 and Fig. 4: add organo-metallic phosphonate nucleator in PLLA/PDLA blend after, t0.5 significantly shortens, and the content of three-dimensional compound crystal obviously increases.In addition, utilize POM to observe (method is the same) spherocrystal pattern, after finding to be added with organic phosphonates nucleator in PLLA/PDLA blend, spherulite size reduces, and nucleation density enlarges markedly.When nucleator addition is 1wt%, t
0.5reduce to 0.65min, effectively can improve working (machining) efficiency, actual forming process requirement can be met, be fully formed the three-dimensional compound crystal of high-melting-point in addition.WAXD test (as Fig. 5) is carried out to its isothermal melting crystallized sample of 140 DEG C, finds, after interpolation 1wt%PPZn, in co-mixing system, only to form three-dimensional compound crystal.
The test result of dynamic properties finds, the storage modulus of modifying material 200 DEG C time of embodiment 1 is 4.53MPa, and the storage modulus of the unmodified material of comparative example 1 200 DEG C time is 0.09MPa, after illustrating that organo-metallic phosphonate nucleator adds, the thermotolerance of material significantly improves.
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 (10)
1. can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, comprise the use of organic metal phosphonic acid salt nucleator, it is characterized in that, concrete preparation process comprises: get poly(lactic acid) matrix, organo-metallic phosphonate nucleator adopts solution or melt blending, and can obtain can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization;
Wherein, the quality of organo-metallic phosphonate nucleator accounts for 0.1% ~ 3% of total composition, and the quality of poly(lactic acid) matrix accounts for 99.9 ~ 97% of total composition, and the mass percent sum of each component is 100%; Described poly(lactic acid) matrix refers to Poly-L-lactic acid (PLLA) and dextrorotation poly(lactic acid) (PDLA), and in poly(lactic acid) matrix, the mass percent of Poly-L-lactic acid is 50% ~ 90%, and the mass percent of dextrorotation poly(lactic acid) is 10% ~ 50%;
Described organo-metallic phosphonate nucleator adopts any one material in phenide phosphonate, phenide phosphinates or phenylbenzene metal phosphinate hydrochlorate.
2. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, when adopting solution blended process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator, be dissolved in easy volatile solvent, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then easy volatile solvent is made to volatilize completely under room temperature, again tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization.
3. according to claim 2 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, described easy volatile solvent adopts methylene dichloride or chloroform.
4. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, when adopting melt-blending process to prepare, concrete grammar is: get Poly-L-lactic acid, dextrorotation poly(lactic acid), organo-metallic phosphonate nucleator add in forcing machine, then mixing 3min at 230 DEG C, extrude pelletizing again, namely obtaining can the high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization.
5. according to claim 4 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, when adopting melt-blending process to prepare, in forcing machine, also can add carbodiimide hydrolysis-resisting agent, Hinered phenols antioxidant.
6. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, the phosphatic structural formula of described phenide is:
Wherein, M is divalent metal.
7. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, the structural formula of described phenide phosphinates is:
Wherein, M is divalent metal.
8. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, the structural formula of described phenylbenzene metal phosphinate hydrochlorate is:
Wherein, M is divalent metal.
9. according to claim 6 to 8 any one can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, described M adopts at least one divalent metal in zinc, barium, calcium.
10. according to claim 1 can the preparation method of high-molecular-weighpolylactic polylactic acid stereoscopic compound material of rapid crystallization, it is characterized in that, the weight-average molecular weight of described Poly-L-lactic acid, dextrorotation poly(lactic acid) is all greater than 80kg/mol, and optical purity is greater than 95%; The particle diameter of organo-metallic phosphonate nucleator is between 10 ~ 30 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410475711.4A CN104262917A (en) | 2014-09-18 | 2014-09-18 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410475711.4A CN104262917A (en) | 2014-09-18 | 2014-09-18 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104262917A true CN104262917A (en) | 2015-01-07 |
Family
ID=52154513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410475711.4A Pending CN104262917A (en) | 2014-09-18 | 2014-09-18 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262917A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700098A (en) * | 2016-12-15 | 2017-05-24 | 浙江大学 | Preparation method of biodegradable supermolecule polylactic acid microspheres |
| CN113667102A (en) * | 2021-08-20 | 2021-11-19 | 浙江大学衢州研究院 | Method for preparing high-molecular-weight polylactic acid based on nucleating agent |
| CN114149668A (en) * | 2022-01-04 | 2022-03-08 | 浙江宏仕达科技股份有限公司 | Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase |
| CN115637032A (en) * | 2021-07-20 | 2023-01-24 | 北京服装学院 | Heat-resistant flame-retardant polylactic acid material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938378A (en) * | 2004-03-30 | 2007-03-28 | 日产化学工业株式会社 | Polylactic acid resin composition |
| CN101602884A (en) * | 2009-06-25 | 2009-12-16 | 浙江海正生物材料股份有限公司 | A kind of heat-resistance polylactic acid composite material and preparation method thereof |
| CN102212257A (en) * | 2011-04-11 | 2011-10-12 | 中国科学院长春应用化学研究所 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
| CN103189446A (en) * | 2010-09-10 | 2013-07-03 | 帝人株式会社 | Stereocomplex polylactic acid film and resin composition |
-
2014
- 2014-09-18 CN CN201410475711.4A patent/CN104262917A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938378A (en) * | 2004-03-30 | 2007-03-28 | 日产化学工业株式会社 | Polylactic acid resin composition |
| CN101602884A (en) * | 2009-06-25 | 2009-12-16 | 浙江海正生物材料股份有限公司 | A kind of heat-resistance polylactic acid composite material and preparation method thereof |
| CN103189446A (en) * | 2010-09-10 | 2013-07-03 | 帝人株式会社 | Stereocomplex polylactic acid film and resin composition |
| CN102212257A (en) * | 2011-04-11 | 2011-10-12 | 中国科学院长春应用化学研究所 | Calcium-carbonate-supported nucleating agent used for poly(lactic acid) crystallization and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700098A (en) * | 2016-12-15 | 2017-05-24 | 浙江大学 | Preparation method of biodegradable supermolecule polylactic acid microspheres |
| CN115637032A (en) * | 2021-07-20 | 2023-01-24 | 北京服装学院 | Heat-resistant flame-retardant polylactic acid material and preparation method thereof |
| CN113667102A (en) * | 2021-08-20 | 2021-11-19 | 浙江大学衢州研究院 | Method for preparing high-molecular-weight polylactic acid based on nucleating agent |
| CN114149668A (en) * | 2022-01-04 | 2022-03-08 | 浙江宏仕达科技股份有限公司 | Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104804388A (en) | Preparation method of high molecular weight polylactic acid material with high stereo-compound content | |
| CN104650548B (en) | The easily preparation method of the poly-lactic acid in high molecular weight material of Stereocomplex crystallization | |
| JP5285834B2 (en) | Method for producing polylactic acid | |
| CN104262917A (en) | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly | |
| US20100004362A1 (en) | POLYLACTIC ACID FIBER AND MANUFACTURING METHOD THEREOF( as amended | |
| EP1970399A1 (en) | Process for producing polyglycolic acid resin composition | |
| JP2016514744A (en) | Polylactic acid stereocomplex composition, molded product thereof, production method thereof and use thereof | |
| TW200909512A (en) | Polylactic acid composition and fiber composed of the same | |
| CN106459390A (en) | Polyester and method for preparing such a polyester | |
| ES2527106T3 (en) | Polylactic Acid Composition | |
| JP2005187626A (en) | Manufacturing process of polylactic acid stereo complex body | |
| EP2285863A1 (en) | Absorbable copolyesters of poly(ethoxyethylene diglycolate) and glycolide | |
| CN111087581B (en) | Method for preparing polyglycolic acid | |
| CN107108901A (en) | It is molded polylactic acid article and preparation method thereof | |
| CN104877317A (en) | Preparation method of full-bio-based composite material capable of being rapidly composited stereoscopically after melting | |
| WO2010087422A1 (en) | Method for producing polylactic acid | |
| CN112321996A (en) | Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof | |
| JP5150074B2 (en) | Polylactic acid and method for producing the same | |
| JP7209828B2 (en) | An integrated manufacturing method for producing polyglycolic acid products | |
| JP3304237B2 (en) | Core / sheath type biodegradable composite fiber | |
| CN102153844A (en) | High-impact heat-resisting polylactic resin with high light transmittance and preparation method of high-impact heat-resisting polylactic resin | |
| JP2008120878A (en) | Polylactide granule and composition containing the same | |
| CN105936742A (en) | Preparation method of low-cost heat-resistant food grade polylactic acid material | |
| CN101296993B (en) | Polylactic acid composition | |
| KR101684924B1 (en) | Manufacturing method of molten cellulose derivative composition and tmolten cellulose derivative using thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150107 |
|
| RJ01 | Rejection of invention patent application after publication |