• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    stereocomplex composition of polylactic acid, its molded product, process for its manufacture and its application. the present invention discloses a stereocomplex polylactic acid composition containing pure stereocomplex crystals and a process for its manufacture. the composition according to this invention comprising (a) from 30 to 70% by weight of poly(l-lactic acid) (pla), (b) from 70 to 30% by weight of poly(d-lactic acid) ( pdla) and (c) from 0.01 to 10% by weight of nucleating agent, which can be obtained by solution and melt mixing. stereocomplex crystals are preferably formed according to the invention, and homocrystals (a crystal form) for the homopolymer of plla or pdla cannot be observed. the melting temperature of the composition according to the invention is at least 200 °C, which is around 30 to 50 °C higher than the homopolymer of plla or pdla.
    公开号:BR112015024199B1
    申请号:R112015024199-9
    申请日:2014-03-19
    公开日:2021-07-27
    发明作者:Xiuqin Zhang；Zujiang Xiong；Guoming LIU；Xia Dong；Tao Wen；Rui Wang；Dujin Wang
    申请人:Institute Of Chemistry, Chinese Academy Of Sciences；Purac Biochem B.V.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention discloses a stereocomplex polylactic acid composition containing pure stereocomplex crystals and a process for its manufacture. The invention also relates to a molded product comprising this composition, a process for manufacturing this composition and its use. BACKGROUND
    [002] Polylactide or poly (lactic acid) (PLA) is a bio-based and biodegradable polymer derived from renewable resources and widely used as an alternative material to fossil-based polymers. Enhancing the thermal stability or heat resistant properties of PLA is a crucial issue to broaden the scope of your industrial and commodity applications.
    [003] After mixing poly (L-lactic acid) (PLLA) with poly (D-lactic acid) (PDLA), a crystalline phase of interest will be formed. A racemic stereocomplex structure in the equimolar mixtures of PLLA and PDLA has been reported, which has been defined as stereocomplex crystals. The melting temperature of stereocomplex crystals is around 50 °C higher than that of pure PLLA or PDLA homocrystals. The PLA stereocomplex is expected to improve several of the properties of PLA-based materials, such as physical properties, thermal properties and resistance to hydrolysis.
    [004] However, the formation of stereocomplexes is affected by many factors, such as the mixing ratio, molecular weight, optical purity of PLLA and PDLA, processing and heat treatment conditions, this means that there is a competitive relationship between the ho - mocrystals (α crystalline form) and stereocomplex crystals under certain conditions. Thus, the PLA stereocomplex which consists exclusively of pure stereocomplex crystals cannot be easily obtained by mixing PLLA and PDLA.
    [005] Recently, several patents have been put into evidence on how to improve the crystallization rate and how to increase the content of stereocomplex crystals. For example, CN 102532837 discloses a method of preparation after melt mixing PLLA and PDLA at a temperature of 140 to 210°C. Although the highest content of stereocomplex crystals is obtained by the disclosed method, the content of stereocomplex crystals decreases and homocrystals appear in subsequent processing.
    [006] In JP 20863356 the stereocomplex crystals are obtained after annealing at a high temperature between the melting point of the homopolymer and the stereocomplex PLA. Crystallinity is very low due to the low crystallization rate.
    [007] In JP2008248022 a diblock copolymer of PLLA and PDLA is synthesized to improve the content of stereocomplex crystals.
    [008] The nucleating agent mixing method is simple, more convenient and efficient to improve the crystallinity of the stereo-complex, compared to lower temperature thermal processing, annealing and synthesizing. In JP2003192884 the crystallization rate is improved by adding a phosphoric ester metal salt to the nucleating agent. CN 18988327 A discloses a composition comprising the PLA stereoblock and an aryl urea derivative, stereocomplex crystals are selected and crystallinity is improved in this method. However, the nucleating agent content is higher, and homocrystals can also be observed in PLLA/PDLA mixtures.
    [009] The inventors have now found that stereocomplex crystals can be selected by adding a specific nucleating agent, and that it is possible to obtain a composition of pure stereocomplex PLA crystals and substantially free of PLA homocrystals. Invention Content
    [0010] The present invention discloses a stereocomplex polylactic acid composition containing pure stereocomplex crystals, which will improve the heat resistance property of PLA-based materials.
    [0011] The present invention discloses a molded product of polylactic acid stereocomplex composition containing pure stereocomplex crystals, with high melting point, high crystallinity and heat resistance properties.
    [0012] The present invention discloses a process for manufacturing a product of polylactic acid stereocomplex composition with pure stereocomplex crystals, and the product will preserve the individual stereocomplex crystals after heat treatment, and with high crystallinity and crystallization rate.
    [0013] The present invention discloses a molded product and its application.
    [0014] The aforementioned technical problems of known compositions, molded products, manufacturing methods and uses can be overcome or at least mitigated by the present invention.
    [0015] The objectives of the present invention are achieved by means of a polylactic acid stereocomplex composition comprising the mixture of PLA and nucleating agent, wherein the nucleating agent is at least that of the aryl amide derivative, the general formula is
    where R 1 is a cycloaliphatic group having 3 to 8 carbon atoms, and where m is an integer ranging from 1 to 6 and includes these values.
    According to a second aspect, there is provided a stereocomplex polylactic acid composition comprising from 0.01 to 10% by weight of nucleating agent and from 90 to 99.99% by weight of PLA mixture, and in that the stereocomplex polylactic acid composition contains pure stereocomplex crystals. The polylactic acid stereocomplex composition preferably comprises from 0.2 to 5% by weight of nucleating agent, and more preferably from 0.5 to 3% by weight. It is preferred that the polylactic acid stereocomplex composition is substantially free of PLA homocrystals.
    According to a third aspect, a stereocomplex polylactic acid composition is provided, wherein the PLA mixture comprises from 30 to 70% by weight of PLLA and from 70 to 30% by weight of PDLA, and preferably 50% by weight by weight of PLLA and 50% by weight of PDLA.
    [0018] According to a fourth aspect, there is provided a stereocomplex polylactic acid composition, wherein R1 in the chemical formula (I) represents a naphthenic group having 5 or 6 carbon atoms, and m is an integer ranging from and including values from 2 to 4. More preferably it is at least one of N,N'-dicyclohexylterephthalamide, and N,N',N"-tricyclo-1,3,5-benzenetricarboxylamide.
    [0019] According to a fifth aspect, a stereocomplex polylactic acid composition is provided, wherein the weighted average molecular weight of at least one of the PLLA and PDLA components is from 10 to 500 kg/mol, and the optical purity of at least one of the PLLA and PDLA components is above 90%, preferably above 98%.
    According to a sixth aspect, a stereocomplex polylactic acid composition is provided, wherein the melting point of the composition is above 200°C, and preferably between 200 and 230°C.
    According to a seventh aspect, a stereocomplex polylactic acid composition is provided, wherein the relative content of the stereocomplex crystals in the crystalline phase is above 95%, and preferably substantially 100%, wherein the crystallization is preferably isothermal at a temperature above 120 °C, more preferably at a temperature between 120 and 140 °C. This was measured by WAXD or by DSC under standard conditions. Both methods gave substantially the same results.
    [0022] According to an eighth aspect, there is provided a molded product containing the stereocomplex polylactic acid composition as described above, said composition preferably comprising from 0.01 to 10% by weight of nucleating agent and from 90 to 99.99 % by weight of PLA blend, wherein the PLA blend comprises PLLA and PDLA. The molded product of the polylactic acid stereocomplex composition preferably comprises from 0.2 to 5% by weight of nucleating agent, and more preferably from 0.5 to 3% by weight.
    According to a ninth aspect, there is provided a molded product containing the stereocomplex polylactic acid composition comprising stereocomplex crystals, wherein the stereocomplex polylactic acid composition contains stereocomplex crystals.
    According to a tenth aspect, there is provided a molded product containing the stereocomplex polylactic acid composition, wherein the PLA mixture comprises from 30 to 70% by weight of PLLA and from 70 to 30% by weight of PDLA, and preferably 50% by weight of PLLA and 50% by weight of PDLA.
    According to an eleventh aspect, there is provided a molded product of the stereocomplex composition of polylactic acid, wherein R1 in the chemical formula (I) represents a naphthenic group having 5 or 6 carbon atoms, in is an integer ranging from and includes the values of 2 to 4. More preferably it is at least one of N,N'-dicyclohexylterephthalamide, and N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxylamide.
    [0026] According to a twelfth aspect, there is provided a molded product of the stereocomplex polylactic acid composition, wherein the weight average molecular weight of at least one of the PLLA and PDLA components is from 10 to 500 kg/mol, and the optical purity of at least one of the PLLA and PDLA components is above 90%, preferably above 98%.
    According to a thirteenth aspect, there is provided a molded product of the polylactic acid stereocomplex composition, wherein the melting point of the composition is above 200°C, and preferably between 200 and 230°C.
    [0028] According to a fourteenth aspect, there is provided a molded product containing a stereocomplex polylactic acid composition, wherein the relative content of the stereocomplex crystals in the crystalline phase is above 95% and preferably substantially 100%, by means of the which crystallization is preferably isothermal at a temperature above 120°C, more preferably at a temperature between 120 and 140°C.
    According to a fifteenth aspect, there is provided a molded product containing a stereocomplex polylactic acid composition, wherein the storage modulus is above 20MPa at 180°C in the DMA curves.
    [0030] According to a sixteenth aspect, a process is provided for the manufacture of a stereocomplex polylactic acid composition, wherein the solution or melt mixture can be selected.
    [0031] According to a seventeenth aspect, a process is provided for the manufacture of a stereocomplex polylactic acid composition, in which the PLLA and PDLA resins are mixed in trichloromethane with a PLLA/PDLA weight ratio ranging from 30 /70 to 70/30, wherein the mixture of 0.01 to 10% by weight (based on the gross weight of PLLA and PDLA) of the nucleating agent (at least one of N,N'-dicyclohexylterephthalamide and N,N ',N'-tricyclo-1,3,5-benzenetricarboxylamide) is added, the mixture being subsequently stirred for 1 to 60 min, after which the mixture is molded onto a surface and dried in vacuum, whereby to compose it. -Pla's stereocomplex position is obtained.
    According to an eighteenth aspect, there is provided a stereocomplex polylactic acid composition or a molded product for application in garment material, food packaging, medical clothing and heat resistant end uses.
    [0033] The present invention has the following advantages:
    [0034] A stereocomplex polylactic acid composition according to the present invention, wherein the relative content of the stereocomplex crystals in the crystalline phase is above 95%.
    [0035] A stereocomplex polylactic acid composition according to the present invention, wherein substantially 100% of the stereocomplex crystals are still present after melting several times.
    [0036] A nucleating agent according to the present invention has properties such as cheapness and lower dosage.
    [0037] A process for manufacturing according to the present invention is simple and feasible.
    [0038] A process for manufacturing according to the present invention is suitable for solution mixing, melt mixing, molding or spinning.
    A stereocomplex polylactic acid composition and its molding product according to the present invention contain pure stereocomplex crystals and substantially no low melting PLA homo-crystal. Stereocomplex crystals are preferably formed according to the invention, and homocrystals (α crystal form) for PLLA or PDLA homopolymers cannot be observed. The melting temperature of the composition according to the invention is higher than that of the individual PLLA or PDLA homopolymers, so that the heat resistance properties of the PLA-based materials improve accordingly. The composition and its molding product contain pure stereo-complex crystals, and the physical properties and hydrolysis resistance of PLA-based materials improve. Description of figures
    [0040] The invention is further illustrated by the attached drawings, in which:
    [0041] FIG. 1 shows the results of differential scanning calorimetry (DSC) during the cooling process of the products of Examples 1, 2 and 3, and Comparative Examples 1, 2, 3, 4, and 5;
    [0042] FIG. 2 shows the DSC results during the heating process of the products of Examples 1, 2 and 3, and Comparative Examples 1, 2, 3, 4 and 5;
    [0043] FIG. 3 shows the DSC results during the heating process after isothermal crystallization of the product of Example 1;
    [0044] FIG. 4 shows the DSC results during the heating process after isothermal crystallization of the product of Example 2;
    [0045] FIG. 5 shows the DSC results during the heating process after isothermal crystallization of the product of Example 3;
    [0046] FIG. 6 shows the DSC results during the heating process after isothermal crystallization of the product of Comparative Example 1;
    [0047] FIG. 7 shows the DSC results during the heating process after isothermal crystallization of the product of Comparative Example 2;
    [0048] FIG. 8 shows the DSC results during the heating process after isothermal crystallization of the product of Comparative Example 3;
    [0049] FIG. 9 shows the DSC results during the heating process after isothermal crystallization of the products of Examples 4 and 5;
    [0050] FIG. 10 shows the DSC results during the heating process after isothermal crystallization of the products of Example 6 and Comparative Example 6;
    [0051] FIG. 11 shows the 2D-WAXS pattern of stereo-complex crystals formed for the products of Examples 1, 2, 3, 4, 5 or 6;
    [0052] FIG. 12 shows the storage modulus E' of PLLA, a stereocomplex polylactic acid composition and its molded product as a function of temperature for the products of Example 18 (curve 1) and 19 (curve 2) and Comparative Example 7 (curve 4) and 8 (curve 3);
    [0053] FIG. 13 shows the enlarged profiles of Fig. 12 in a higher temperature region.
    [0054] The invention is further illustrated by the following non-limiting Examples. Example 150/50, of PLLA/PDLA, 0.5% by weight of N,N'-dicyclohexylterephthalamide for the nucleating agent
    The stereocomplex polylactic acid composition was prepared using PLLA from Purac Biochem BV, characterized by Mw = 177 kg/mol, Mn = 116 kg/mol, polydispersity, DPI = 1.53, optical purity > 99%, Tm = 174 °C and Tg = 61 °C (DSC, 10 °C/min); PDLA from Purac Biochem BV, characterized by Mw = 167 kg/mol, Mn = 108 kg/mol, polydispersity, DPI = 1.56, optical purity > 98%, Tm = 174 °C and Tg = 61 °C (DSC, 10°C/min); N,N'-dicyclohexilt erephthalamide as the nucleating agent of Shanxi Provincial Institute of Chemical Industry, China, Tm > 300 °C. Materials were vacuum dried at 80 °C for 24 h before processing.
    [0056] Solution mixture: equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dl for 30 min, and 0.5% by weight (based on the gross weight of PLLA and PDLA) of the nucleating agent N,N'-dicyclohexylterephthalamide was added, then rapidly stirred for approximately 2 h. The mixtures were molded onto a culture dish and vacuum dried at 80°C for 3 days.
    [0057] The behavior of non-isothermal crystallization was measured by DSC on a TA Instruments Q2000. DSC scans were obtained in the cooling processes from 250 °C to 50 °C and in the following second heating process to 250 °C. The sample was heated to 250 °C to melt any existing crystallinity prior to cooling. Cooling/heating rates were 10 °C/min under nitrogen atmosphere. The results are shown in Figs. 1 and 2, and Table 1.
    [0058] The isothermal crystallization behavior was measured by DSC on a TA Instruments Q2000. Typically, crystallization half-times were obtained after isothermal crystallization at different temperatures by quenching the molten sample from 250 °C to the isothermal crystallization temperature, while it was first heated to 250 °C to dissolve any crystallinity. existing. Crystallinity was allowed to develop at these fixed crystallization temperatures. The sample was subsequently heated at 10 °C/min to 250 °C. The results are shown in Fig. 3 and Table 2. Example 250/50, PLLA/PDLA, 3% by weight N,N'-dicyclohexylterephthalamide for nucleating agent
    [0059] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dl for 30 min, and 3% by weight (based on the gross weight of PLLA and PDLA) of the N-nucleating agent ,N'-dicyclohexylterephthalamide was added. The method for sample preparation is similar to Example 1.
    [0060] The composition containing 3% by weight of N,N'-dicyclohexylterephthalamide shows an exothermic peak of crystallization at 147 °C during the cooling process, and a single melting peak for the melting of the stereocomplex crystals in the heating process can be seen around 210 °C, the heat fusion is around 48.5 J/g. The DSC results for the cooling and heating processes show that the N,N'-dicyclohexylterephthalamide nucleator can exclusively nucleate the stereocomplex crystals.
    [0061] The non-isothermal and isothermal crystallization behaviors were measured by DSC as described in Example 1, and the results are shown in Figs. 1, 2 and 4, and in Tables 1 and 2. Example 350/50, of PLLA/PDLA, 0.25% by weight of N,N'-dicyclohexyl terephthalamide and 0.25% by weight of N,N ',N"-tricyclohexyl amide for nucleating agents
    [0062] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dl for 30 min, and 0.25% by weight of N,N'-dicyclohexyl terephthalamide and 0.25% by weight of N,N',N"-tricyclohexyl trimesic amide (Based on gross weight of PLLA and PDLA were added. Method for sample preparation is similar to Example 1.
    The composition containing 0.25% by weight of N,N'-dicyclohexyl terephthalamide and 0.25% by weight of N,N',N"-tricyclohexyl trimesic amide shows an exothermic peak of crystallization at 129°C during the cooling process, and a single melting peak for the melting of stereocomplex crystals in the heating process can be seen around 212 °C, the heat melting is around 49.4 J/g. in the cooling and heating processes show that the nucleators of the compound of N,N'-dicyclohexyl terephthalamide and N,N',N"-tricyclohexyl trimesic amide can exclusively nucleate the stereocomplex crystals.
    [0064] The non-isothermal and isothermal crystallization behaviors were measured by DSC as described in Example 1, and the results are shown in Figs. 1, 2 and 5, and in Tables 1 and 2. Example 430/70, PLLA/PDLA, 3% by weight N,N'-dicyclohexylterephthalamide for nucleating agent
    [0065] PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dL for 30 min at a ratio of 30/70, and 3% by weight (based on the gross weight of PLLA and PDLA) of the N,N'-dicyclohexylterephthalamide nucleating agent was added. The method for sample preparation was similar to Example 1.
    [0066] The behavior of non-isothermal crystallization was measured by DSC as described in Example 1, and the result is shown in Fig. 9. Example 570/30, PLLA/PDLA, 3% by weight N,N'-dicyclohexylterephthalamide for nucleating agent
    [0067] PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dL for 30 min at a ratio of 70/30, and 3% by weight (based on the gross weight of PLLA and PDLA) of the agent N,N'-dicyclohexylterephthalamide nucleation was added. The method for sample preparation was similar to Example 1.
    [0068] The behavior of non-isothermal crystallization was measured by DSC as described in Example 1, and the result is also shown in Fig. 9. Example 650/50, PLLA/PDLA, 1.5 wt% N,N'-dicyclohexyl terephthalamide and 1.5 wt% N,N',N"-tricyclohexyl amide for the nucleating agents
    [0069] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dl for 30 min, and 1.5% by weight of N,N'-dicyclohexyl terephthalamide and 1.5% by weight of N,N',N"-tricyclohexyl trimesic amide (based on gross weight of PLLA and PDLA) were added. The method for sample preparation was similar to Example 1.
    [0070] The behavior of non-isothermal crystallization was measured by DSC as described in Example 1, and the result is shown in Figure 10 and Table 1. Examples 7 to 17
    [0071] The method of Examples 7 to 11 for sample preparation was similar to Example 1, and the method of Examples 12 to 17 for sample preparation was similar to Example 6, and the weight percentages of all components were as follows:

    [0072] Citing N,N'-dicyclohexyl terephthalamide (R1 = 6 in = 2) as an example, the method of preparation was as follows: N,N'-dicyclohexyl terephthalamide was synthesized with paraphthaloyl chloride and cyclohexane as the materials. The reaction was carried out in an inert solvent and at a certain temperature under stirring. The paraphthaloyl chloride material was obtained with terephthalic acid as the materials through the sulfoxide chloride method. The CAS number of N,N'-dicyclohexyl terephthalamide is 15088-29-6.
    [0073] The results of FT-IR, 13C NMR and 1H NMR showed that the above structure was indeed obtained. Example 18
    [0074] The method of Example 18 for preparing molded products was similar to Example 1 or 6. The dynamic mechanical properties were investigated using a DMA dynamic mechanical analyzer. The strip-shaped samples (10 mm x 6 mm x 1.8 mm) were measured in traction mode at a constant frequency of 1.0 Hz as a function of temperature from 20 to 250 °C at a heating rate of 3 °C/minute under a nitrogen flow, and the result is shown in Fig.12. Example 19
    [0075] The method of Example 19 for preparing molded products was similar to Example 2. The dynamic mechanical properties were investigated using a DMA dynamic mechanical analyzer. The strip-shaped samples (10 mm x 6 mm x 1.8 mm) were measured in traction mode at a constant frequency of 1.0 Hz as a function of temperature from 20 to 250 °C at a heating rate of 3 °C/minute under nitrogen flow, and the result is shown in Fig.12. Comparative Example 150/50, PLLA/PDLA
    [0076] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dL for 2 h, no nucleating agent was added. The method for sample preparation was similar to Example 1.
    [0077] The non-isothermal and isothermal crystallization behaviors were measured by DSC as described in Example 1, and the results are shown in Figs. 1, 2 and 6, and Tables 1 and 2. Comparative Example 250/50, PLLA/PDLA, 0.5% by weight of montmorillonite as the nucleating agent
    [0078] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dL for 2 h, 0.5% by weight (based on the gross weight of PLLA and PDLA) of montmorillonite was added. The method for sample preparation was similar to Example 1.
    The non-isothermal and isothermal crystallization behaviors were measured by DSC as described in Example 1, and the results are shown in Figs. 1, 2 and 7, Tables 1 and 2. Comparative Example 350/50, of PLLA / PDLA, 0.5% by weight of talc as the nucleating agent
    [0080] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dL for 2 h, 0.5% by weight (based on the gross weight of PLLA and PDLA) of the nucleating agent. mineral talc was added. The method for sample preparation was still similar to Example 1.
    [0081] The non-isothermal and isothermal crystallization behaviors were measured by DSC as described in Example 1, and the results are shown in Figs. 1, 2 and 8, Tables 1 and 2. Comparative Example 4 100% PLLA
    [0082] PLLA resin was dissolved in trichloromethane at a polymer concentration of 2 g/dL for 2 h, no nucleating agent was added. The method for sample preparation was similar to Example 1.
    [0083] The non-isothermal crystallization behavior was measured by DSC as described in Example 1, and the results are shown in Figs. 1 and 2, and Table 1. Comparative Example 5100% PLLA, 3% by weight N,N'-dicyclohexylterephthalamide as nucleating agent
    [0084] PLLA resin was dissolved in trichloromethane at a polymer concentration of 2 g/dl for 2 h, 3% by weight (based on PLLA weight) of the nucleating agent N,N'-dicyclohexylterephthalamide was added. The method for sample preparation was similar to Example 1.
    [0085] The non-isothermal crystallization behavior was measured by DSC as described in Example 1, and the results are shown in Figs. 1 and 2, and Table 1. Comparative Example 650/50, PLLA/PDLA,
    [0086] Equimolar PLLA and PDLA were dissolved in trichloromethane at a polymer concentration of 2 g/dl for 30 min, no nucleating agent was added. The method for sample preparation was similar to Example 6 above.
    [0087] The non-isothermal crystallization behavior was measured by DSC as described in Example 1, and the result is shown in Figure 10 and Table 1. Comparative Example 7
    [0088] The method of Comparative Example 7 for preparing molded products was similar to Comparative Example 4. The dynamic mechanical properties were investigated using a DMA dynamic mechanical analyzer. Strip-shaped samples (10 mm x 6 mm x 1.8 mm) were measured in traction mode at a constant frequency of 1.0 Hz as a function of temperature from 20 to 250 oC at a heating rate of 3 °C/min under nitrogen flow, and the result is shown in Fig.12. Comparative Example 8
    [0089] The method of Comparative Example 8 for preparing molded products was similar to Comparative Example 1 or 6. The dynamic mechanical properties were investigated using a DMA dynamic mechanical analyzer. Samples in the form of strips (10 mm x 6 mm x 1.8 mm) were measured in traction mode at a constant frequency of 1.0 Hz as a function of temperature from 20 to 250 °C, at a rate of heating of 3 °C/minute under a nitrogen flow, and the result is shown in Fig.12.
    [0090] The DSC results of the non-isothermal crystallization during the cooling and according to the heating and isothermal crystallization processes are shown in Fig. 1, 2 and Tables 1 and 2.

    Remarks: t, the crystallization half-time.
    [0091] Stereocomplex crystals are preferably formed in compositions containing N,N'-dicyclohexylterephthalamide and/or N',N',N"-tricyclohexyltrimesicamide according to the invention (Examples 1, 2 and 3), and homocrystals (one crystal form) for the PLLA or PDLA homopolymer cannot be observed. The selected 2D WAXS patterns of the composition are shown in Fig. 11, the crystalline planes (110), (300)/(030) and (220) of the form of stereocomplex crystals can be seen, confirming that the only sample crystallized as a pure stereocomplex crystal (sc-crystal) However, there are obvious exothermic peaks around 130 °C during cooling and the endothermic peak around 165° C during the second heating process for the crystallization of homocrystals and melting in the sample of Comparative Examples 1, 2 and 3, homocrystals appear in the cooling and heating processes, coexisting with the stereocomplex crystals in the sample. O effect of the nucleator with homocrystals, the crystallization behavior of the mixture of PLLA and PLLA/N,N'-dicyclohexylterephthalamide (Comparative Examples 4 and 5) was also investigated (Figs. 1 and 2). As it cools down from 250 oC, no peak is observed during the cooling process for the two samples, which means that the crystallization capacity of PLLA is weaker no matter which nucleating agent has been added. The DSC results show that the nucleating agent selected from N,N'-dicyclohexylterephthalamide and/or N,N',N"-tricyclohexyltrimessicamide can selectively nucleate stereocomplex crystals.
    [0092] The results of isothermal crystallization at different temperatures are shown in Figs. 3 to 10, and Table 2, indicating that the crystallization half-time of the composition of the present invention (Examples 1 to 5) is noticeably short, and only a single peak in the heating process for the stereocomplex crystals shown around 210 °C after isothermal crystallization at a temperature above 120 °C, even for the non-equimolar mixtures of PLLA and PDLA and the product molded through the melt mixture (Example 6). However, compositions containing mineral talc or montmorillonite or without nucleator (Comparative Examples 1 , 2 and 3) present two peaks in the heating process for homocrystals and stereocomplex crystals, respectively, present at approximately 166 and 215 °C after isothermal crystallization at a temperature below 160 oC.
    [0093] The high content of PLA stereocomplex crystals and the product with high heat resistance properties can be obtained with the material according to the present invention. The PLLA storage modulus E' curves, a stereo-complex composition of polylactic acid and its molded product as a function of temperature for the products of Example 18 (curve 1) and 19 (curve 2) and Comparative Example 7 (curve 4) and 8 (curve 3) are shown in Figs. 12 and 13. Samples from Examples 18 and 19 show the highest storage modulus above 180 °C, more than twice the E' value of Comparative Example 8. However, the pure PLLA sample (Comparative Example 7 ) melts at this temperature, as a result the value of storage module E' drops to zero.
    [0094] The present invention discloses a stereocomplex polylactic acid composition that can be used for solution mixing, melt mixing, molding or spinning. Stereocomplex PLA product with high melting point, high heat resistance properties, and high content of pure stereocomplex crystals, can be obtained with the disclosed composition. A stereo-complex polylactic acid composition according to the present invention can be applied in agricultural and garment material, in food packaging, building material, medical clothing and production for other heat resistant end uses.
    权利要求:
    Claims (21)
    [0001]
    1. A stereocomplex polylactic acid composition comprising: a blend of PLA containing poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA); and a nucleating agent, characterized in that the nucleating agent is an aryl amide derivative having the general formula (I)
    [0002]
    2. Polylactic acid stereocomplex composition according to claim 1, characterized in that it comprises from 0.01 to 10% by weight of nucleating agent and from 90 to 99.99% by weight of PLA mixture, and in that the stereocomplex polylactic acid composition contains pure stereocomplex crystals.
    [0003]
    3. Polylactic acid stereocomplex composition according to claim 2, characterized in that the PLA mixture comprises from 30 to 70% by weight of PLLA and from 70 to 30% by weight of PDLA.
    [0004]
    4. Polylactic acid stereocomplex composition according to claim 3, characterized in that the PLA mixture comprises 50% by weight of PLLA and 50% by weight of PDLA.
    [0005]
    5. A stereocomplex polylactic acid composition according to any one of claims 1 to 4, characterized in that R1 in chemical formula (I) represents a naphthenic group with 5 or 6 carbon atoms.
    [0006]
    6. A stereocomplex polylactic acid composition according to any one of claims 1 to 5, characterized in that the nucleating agent is N,N'-dicyclohexylterephthalamide, and said composition optionally further comprises N,N',N"- tricyclohexyl-1,3,5-benzenetricarboxylamide.
    [0007]
    7. Polylactic acid stereocomplex composition according to any one of claims 1 to 6, characterized in that it comprises from 0.2 to 5% by weight of nucleating agent.
    [0008]
    8. Polylactic acid stereocomplex composition according to claim 7, characterized in that it comprises from 0.5 to 3% by weight of nucleating agent.
    [0009]
    9. A stereocomplex polylactic acid composition according to any one of claims 1 to 8, characterized in that the weighted average molecular weight of at least one of the PLLA and PDLA components is 10 to 500 kg/mol, and the optical purity of at least one of the PLLA and PDLA components is above 90%.
    [0010]
    10. A stereocomplex polylactic acid composition according to any one of claims 1 to 8, characterized in that the weighted average molecular weight of at least one of the PLLA and PDLA components is 10 to 500 kg/mol, and the optical purity of at least one of the PLLA and PDLA components is above 98%.
    [0011]
    11. A stereocomplex polylactic acid composition according to any one of claims 1 to 10, characterized in that the melting point of the composition, as determined by Differential Scanning Calorimetry (DSC) under heating at a rate of 10°C/ min, is between 200 and 300 oC.
    [0012]
    12. Polylactic acid stereocomplex composition according to any one of claims 1 to 11, characterized in that the relative content (mass/mass) of the stereocomplex crystals in relation to the total crystalline phase present in the stereocomplex composition is above 95%.
    [0013]
    13. A stereocomplex polylactic acid composition according to claim 12, characterized in that the relative content (mass/mass) of the stereocomplex crystals in relation to the total crystalline phase is 100%.
    [0014]
    14. Polylactic acid stereocomplex composition according to claim 12 or 13, characterized in that the composition is obtained by isothermal crystallization at a temperature between 120 and 140°C.
    [0015]
    15. Molded product, characterized in that it comprises a PLA composition as defined in any one of claims 1 to 14.
    [0016]
    16. Product molded according to claim 15, characterized in that the melting point of the composition is between 200 to 230 oC, and the melting enthalpy range ΔHm is between 45 and 60 J/g, where the point melting rate of the composition is determined by Differential Scanning Calorimetry (DSC) at a rate of 10°C/min which is applied during a second heating process, said second heating process being carried out after a first heating of the composition to 250° C followed by cooling to 50°C.
    [0017]
    17. Product molded according to claim 15 or 16, characterized in that the storage module is between 20 MPa and 60 MPa at 180 oC in the Dynamic Mechanical Analyzer (DMA) curves.
    [0018]
    18. Molded product according to any one of claims 15 to 17, characterized in that it is for the application of clothing material, food packaging, medical cloth and heat resistant end uses.
    [0019]
    19. Process for the manufacture of a composition as defined in any one of claims 1 to 14, characterized in that the solution or the molten mixture is selected.
    [0020]
    20. Process for the manufacture according to claim 19, characterized in that the PLLA and PDLA resins are mixed in trichloromethane with a PLLA/PDLA weight ratio ranging from 30/70 to 70/30, in which the 0.01 to 10% by weight mixture (based on the gross weight of PLLA and PDLA) of the nucleating agent is added, the mixture being subsequently stirred for 1 to 60 min, after which the mixture is melted onto a surface and dried in vacuo, whereby the stereocomplex polylactic acid (PLA) composition is obtained.
    [0021]
    21. A stereocomplex polylactic acid composition according to any one of claims 1 to 14, characterized in that they are for application in garment material, food packaging, medical clothing and heat resistant end uses.
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    同族专利:
    公开号 | 公开日
    CN104059343A|2014-09-24|
    JP6174238B2|2017-08-02|
    KR102181699B1|2020-11-24|
    US9644095B2|2017-05-09|
    BR112015024199A2|2017-07-18|
    KR20160026843A|2016-03-09|
    WO2014147132A1|2014-09-25|
    US20160272811A1|2016-09-22|
    JP2016514744A|2016-05-23|
    EP2976374A1|2016-01-27|
    CN104059343B|2016-08-31|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201310090619.1|2013-03-20|
    CN201310090619.1A|CN104059343B|2013-03-20|2013-03-20|A kind of polylactic acid composition and moulded products thereof, preparation method, and application thereof|
    PCT/EP2014/055517|WO2014147132A1|2013-03-20|2014-03-19|A polylactic acid stereocomplex composition, its molded product, a process for its manufacture and its application|
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