AU2019100618A4 - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polylactic acid composite material and a preparation method thereof, and belongs to the technical field of polymer modified materials. The polylactic acid composite material of the invention comprises the following preparation materials: 55-80 parts of polylactic acid, 10~35 parts of talcum powder, 0~5 parts of calcium carbonate, 0~10 parts of toughening agent, processing aid 0~ 10 parts; wherein the polylactic acid is composed of (a) amorphous polylactic acid and (b) crystalline or semi-crystalline polylactic acid; the polylactic acid composite material uses amorphous polylactic acid as a continuous phase, the crystalline or semi-crystalline polylactic acid as a crystal phase, and the average size of the crystal phase in the polylactic acid composite material is not more than 1 pm. In the invention, the amorphous polylactic acid is used as the continuous phase, the crystalline or semi-crystalline polylactic acid is used as the crystalline phase, and the average crystal size of the polylactic acid composite material is controlled to be no more than 1 m, thereby obtaining the polylactic acid composite material with significant improvement the notched impact strength and higher heat distortion temperature.
Description
Polylactic acid composite material and preparation method thereof
Technical field
The invention relates to a polylactic acid composite material and a preparation method thereof, and belongs to the technical field of polymer modified materials.
Background technique
Polylactic acid resin is a polymer material obtained by chemical synthesis or biosynthesis using lactic acid as a monomer, and its raw materials are mainly corn, potato and the like. Polylactic acid resins are inexpensive, and because their raw materials are natural crops, carbon emissions are minimal. From the safety point of view, polylactic acid is non-toxic and non-irritating, has excellent transparency and biodegradability, and is easily catabolized by various microorganisms or enzymes in animals and plants in nature, eventually forming carbon dioxide and water, thus to a certain extent. It reduces white pollution and is an ideal green polymer material.
However, polylactic acid has the disadvantages of brittleness, poor impact resistance, low mechanical strength of amorphous polymer, and high cost, which limits its application range. In addition, the thermal stability of polylactic acid is poor, and even under conditions of lower than the melting temperature and thermal decomposition temperature, the molecular weight during processing is greatly reduced due to degradation, resulting in a decrease in mechanical properties of the polymer. In order to overcome the above disadvantages, especially in order to improve the toughness of the polylactic acid material, a method of toughening polylactic acid may be employed, mainly including blending, compounding, copolymerization, plasticizing, and the like. Cohn et al. used a two-step process to produce a polycaprolactone-PLA multi-block copolymer. The mechanical properties of the copolymer increased with the relative molecular weight of the PLA segment, and the elongation at break reached 600% (Cohn D, Designing biodegradable multi-block PCL/PLA thermoplastic elastomers, Biomaterials, 2005: 2297~2305). Zhang Wei blends hyperbranched polyamide ester (HBP) with polylactic acid to prepare high-toughness polylactic acid composites (Zhang Wei et al., Research on Toughening Modification of Polylactic Acid by Hyperbranched Polyester Ester, Synthetic Fiber, 2008: 9~11).
Summary of the invention
The object of the present invention is to provide a polylactic acid composite material having high notched impact strength and heat distortion temperature and a preparation method thereof, which overcome the deficiencies of the prior art.
In order to achieve the above object, the technical solution adopted by the present invention is: a polylactic acid composite material comprising the following raw materials by weight: 55-80 parts of polylactic acid, 10~35 parts of talcum powder, 0~5 parts of calcium carbonate , the toughening agent is 0 to 10 parts, and the processing aid is 0 to 4 parts; wherein the polylactic acid is composed of (a) amorphous polylactic acid and (b) crystalline or semi-crystalline polylactic acid; The composite material has a non-crystalline polylactic acid as a continuous phase, a crystalline or semi-crystalline polylactic acid as a crystalline phase, and an average size of a crystalline phase in the polylactic acid composite material is not more than 1 pm.
Pure crystalline or semi-crystalline polylactic acid can form larger spherulites at a suitable crystallization temperature and a sufficiently long crystallization time, and polylactic acid
2019100618 08 Jun 2019 composites having large spherulites are subjected to impact due to large The spherulites of the size do not absorb the external energy well and are prone to brittle fracture, and the material toughness is poor.
When the size of the crystal phase in the polylactic acid composite material is appropriate and the distribution is uniform, the dispersed polylactic acid crystal is likely to form voids or debonding when subjected to an impact. The void of the crystalline phase polylactic acid corresponds to stress concentration, resulting in yielding of the matrix. Particle formation and void formation creates a new stress distribution that promotes the onset of plastic deformation of the matrix. Plastic deformation can effectively dissipate the fracture energy and cause a high increase in impact strength.
The glass transition temperature Tg of crystalline or semi-crystalline polylactic acid is about 55 ° C. Due to the large steric hindrance of polylactic acid molecular chain structure, polylactic acid is difficult to crystallize under normal temperature or conventional processing conditions, so the heat distortion temperature is usually only About 55 °C. On the other hand, for amorphous polylactic acid, its thermal deformation temperature is lower due to its amorphous structure, and agglomeration usually occurs at about 55 ° C, which is difficult to apply.
In the present invention, the crystalline or semi-crystalline polylactic acid is used as the crystal phase (the crystal is correspondingly the dispersed phase), the amorphous polylactic acid is used as the continuous phase, and the average size of the crystalline phase in the polylactic acid composite material is limited to not more than 1 pm, which is not only advantageous. When polylactic acid crystallizes, it forms finer crystal grains with more uniform distribution, which prevents brittle fracture when the material is impacted; and the uniformly distributed crystal is more favorable for absorbing external impact energy and improving the impact strength of the material. In addition, due to the improvement of the crystallization ability, the heat distortion temperature of the material is also improved. Therefore, the polylactic acid composite of the present invention has significantly improved notched impact strength and higher heat distortion temperature.
The polylactic acid composite material of the invention can be processed into an injection molded part, a blister part and a wire by means of injection molding, plastic absorbing and extrusion.
It is to be noted that the present invention measures the average size of the crystalline polylactic acid crystal phase as a crystal phase in the polylactic acid composite material in a cross section with respect to the direction of the extrusion flow or in the direction of the material output. Thus, the average size of the crystalline polylactic acid crystal phase as the dispersed phase was measured on the two-dimensional shape obtained from the cross section.
The average size of the crystalline polylactic acid crystal phase as the dispersed phase described above is calculated as a numerical average of the particle size of the dispersed phase. In the case of spherical particles, the particle size corresponds to the diameter of the circle.
In the case of non-spherical particles, the particle size (d) is calculated according to the following formula:
d=(dl-d2)l/2
Wherein dl is the small diameter of the ellipse to which the particle can be inscribed or approximated, and d2 is the large diameter.
The selective etching of the amorphous polylactic acid continuous phase can be advantageously
2019100618 08 Jun 2019 carried out by using THF as an etchant at an etching temperature of 25 ° C for 30 minutes, and the unetched portion is a crystalline phase. Polylactic acid.
As a preferred embodiment of the polylactic acid composite material of the present invention, the average size of the crystal phase in the polylactic acid composite material is not more than 0.8 pm. More preferably, the average size of the crystalline phase in the polylactic acid composite material is not more than 0.5 pm. Studies have shown that when the average size of the crystalline phase in the polylactic acid composite material is not more than 0.8 pm, the obtained polylactic acid composite material has better notched impact strength and heat distortion temperature performance; the average size of the crystalline phase in the polylactic acid composite material When it is not more than 0.5 pm, the obtained polylactic acid composite material is most excellent in notched impact strength and heat distortion temperature performance.
In a preferred embodiment of the polylactic acid composite material according to the present invention, the crystalline or semi-crystalline polylactic acid contains 95% by weight or more of L-lactic acid; and the amorphous polylactic acid contains 12% by weight or more. D-lactic acid. The polylactic acid obtained by ring-opening polycondensation of lactide is usually a mixture of polylactic acid polymers containing L-lactic acid and D-lactic acid. When the D-lactic acid content in the polylactic acid exceeds 10%, the polylactic acid is usually amorphous polylactic acid, and the material is soft; and when the D-lactic acid content in the polylactic acid is less than 5%, the polylactic acid has better crystallization. The effect is that it is easy to form spherulitic particles which are uniformly dispersed.
As a preferred embodiment of the polylactic acid composite material of the present invention, in the polylactic acid, the weight percentage of the crystalline or semi-crystalline polylactic acid is 65% to 95%, and the weight percentage of the amorphous polylactic acid is 5%. 35%.
As a more preferred embodiment of the polylactic acid composite material of the present invention, in the polylactic acid, the weight percentage of the crystalline or semi-crystalline polylactic acid is 75% to 85%, and the weight percentage of the amorphous polylactic acid is 15%. -25%.
As a preferred embodiment of the polylactic acid composite material of the present invention, at least one of the following (a) to (d):
(a) the talc powder has an average particle diameter D50 of 5 ~ 13 pm;
(b) the calcium carbonate has an average particle diameter D50 of 1 ~ 7 pm;
(c) the toughening agent is an aliphatic polyester or an aliphatic-aromatic copolyester;
(d) The processing aid is at least one of a mold release agent, a surfactant, a wax, an antistatic agent, a dye, a nucleating agent, and an antioxidant.
As a filling material, talc powder can improve the mechanical properties of polylactic acid composite materials. The particle size of talc powder is too large, the nucleation effect is weak, the crystallinity of polylactic acid composite material is low, the heat resistance temperature is not high, and the particle size of talc powder is too small. It is not easy to disperse in the polymer during processing, causing powder agglomeration, affecting the nucleation effect of talc powder and the impact performance of polylactic acid composite material, and the smaller the particle size of talc powder, the higher the price, the lower the cost performance of the product. Considering the nucleation of talc powder and the heat resistance temperature and impact properties of polylactic acid composites, the average particle size D50 of talc powder is selected
2019100618 08 Jun 2019 to be 5 ~ 13μηι.
The calcium carbonate particles are spherical particles, and the presence of spherical particles can play a certain lubricating role. When the material is impacted by an external force, the slip of the spherical particles can weaken the impact energy of the external force to some extent. Similar to talc powder, the particle size of calcium carbonate is too large, and the lubricating effect is weak; the particle size of calcium carbonate is too small, and it is not easy to disperse in the polymer during processing, resulting in powder agglomeration. In order to optimize the lubricating action of calcium carbonate and to easily disperse in the polymer, the inventors chose calcium carbonate to have an average particle diameter D50 of 1 to 7 pm.
Different processing aids will have different effects on the properties of polylactic acid composites. For example, dyes will change the color of polylactic acid composites, and antioxidants can enhance the oxidation resistance of polylactic acid composites. In practical applications, specific processing aids or processing aid combinations, as well as specific processing aids, can be selected according to actual performance requirements. As a preferred embodiment of the polylactic acid composite material of the present invention, the release agent is: silicone masterbatch, montan wax, erucic acid amide or oleic acid amide; the surfactant is polysorbate, palm At least one of an acid ester and a lauric acid ester; the wax is at least one of erucamide, stearic acid amide, behenic acid amide, beeswax, and beeswax; the antistatic agent is a permanent antistatic agent Preferably, at least one of PELESTAT-230, PELESTAT-6500, and SUNNICO ASA-2500; the dye is at least one of carbon black, black species, titanium dioxide, zinc sulfide, indigo blue, and fluorescent orange; The antioxidant is at least one of a main antioxidant and a secondary antioxidant; the nucleating agent is sodium carbonate, sodium hydrogencarbonate, a metal salt of a monocarboxylic acid, a metal salt of benzoic acid, and an organic phosphorus compound. At least one of a metal salt, an alkali metal salt of a polyester oligomer.
As a preferred embodiment of the polylactic acid composite material of the present invention, the polylactic acid composite material further includes a plasticizer, and the plasticizer is 0.5 to 5 parts by weight. The addition of plasticizer to the polylactic acid helps to promote the movement of the polylactic acid segment, thereby improving the toughness of the polylactic acid composite to a certain extent. As a more preferred embodiment of the polylactic acid composite material of the present invention, the plasticizer is glycerin, polyglycerin, ethylene glycol, PEG-400, PEG-600, PEG-800, epoxidized soybean oil, citric acid ester At least one of acetyl citrate, triacetyl glyceride, and dioctyl adipate. The plasticizers are all low molecular weight compounds, which are liquid at room temperature, and the low molecular weight plasticizer can more effectively promote the crystallization of the polylactic acid and, to some extent, increase the heat resistant temperature of the polylactic acid.
In addition, the present invention also provides a method for preparing the above polylactic acid composite material, which comprises the following steps:
(1) Weighing the components other than talc in the polylactic acid composite material, mixing them uniformly, putting them into a twin-screw extruder, extruding and granulating to obtain a master batch;
(2) The masterbatch obtained in the step (1) is added to the twin-screw extruder in the manner of main feeding, and the talc powder is added into the twin-screw extruder in a side feeding manner, and extruded and granulated to obtain polylactic acid. Composite material.
2019100618 08 Jun 2019
Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention uses crystalline or semi-crystalline polylactic acid as the continuous phase, amorphous polylactic acid as the dispersed phase, and the average particle of the amorphous polylactic acid particles used at the same time. The diameter of the polylactic acid composite material obtained is not more than 1 pm, and the polylactic acid composite material thus obtained has a markedly increased notched impact strength and a high heat distortion temperature.
Detailed ways
The present invention will be further described with reference to specific embodiments in order to better illustrate the objects, aspects and advantages of the invention.
Example 1
An embodiment of the polylactic acid composite material of the present invention, the polylactic acid composite material of the present embodiment uses amorphous polylactic acid as a continuous phase, and crystalline or semi-crystalline polylactic acid as a crystalline phase, and its constituent components are as follows. 1 is shown.
The preparation method of the polylactic acid composite material of the embodiment is:
(1) Weighing the components other than talc in the polylactic acid composite material, mixing them uniformly, extruding and granulating by a co-rotating twin-screw extruder (Coperion) to obtain a master batch; wherein, the double-screw extrusion The screw diameter of the machine is 26mm, the aspect ratio is 40, and the extrusion temperature is 130~210°C;
(2) The masterbatch obtained in the step (1) is fed into the twin-screw extruder in a main feeding manner (from the Oth region of the twin-screw extruder) while the talc powder is side-fed (squeezed from the double helix) The fourth zone of the machine is added to the twin-screw extruder, and dispersed in the fifth and sixth regions of the twin-screw extruder, and the volatile matter is removed in the seventh region and the eighth region, in the ninth region. Extrusion granulation was carried out to obtain a polylactic acid composite material.
After obtaining the above polylactic acid composite material, the notched impact strength is tested according to ASTM D256, and the polylactic acid composite material is made into a spline for measuring the heat distortion temperature by using an injection molding machine (at the time of preparation, the injection temperature is 170 to 230 ° C, and the mold is molded. Temperature 90~120 ° C, cooling time 60~90 s), heat distortion temperature HDT of the spline prepared according to ASTM D648 (test conditions: 0.45 MPa, 6.4 mm, side discharge). The test results are shown in Table 1.
Example 2~5
The composition and properties of the polylactic acid composite materials described in Examples 2 to 5 are as shown in Table 1. The preparation methods and performance test methods of the polylactic acid composite materials described in Examples 2 to 5 are the same as those in Example 1.
Table 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | ||
| Polylactic acid | Average size of crystal phase /pm | 0.99 | 0.8 | 0.5 | 0.4 | 0.75 |
2019100618 08 Jun 2019
| Percentage of non-crystalline polylactic acid in polylactic acid /wt% | 5 | 15 | 20 | 25 | 35 | |
| Percentage of crystalline or semi-crystalline polylactic acid in polylactic acid /wt% | 95 | 85 | 80 | 75 | 65 | |
| Percentage of L-lactic acid in crystalline or semi-crystalline polylactic acid/wt% | 95 | 95 | 98 | 98 | 98 | |
| Percentage of D-lactic acid in amorphous polylactic acid/wt% | 12 | 12 | 12 | 15 | 15 | |
| Parts by weight | 55 | 80 | 60 | 70 | 80 | |
| Talcum powder | Average particle size D50/pm | 5 | 13 | 7 | 9 | 11 |
| Parts by weight | 10 | 35 | 15 | 20 | 25 | |
| Calcium carbonate | Average particle size D50/pm | ___ | 1 | 3 | 5 | 7 |
| Parts by weight | 0 | 5 | 2 | 2 | 4 | |
| Plasticizer | Substance | glycerin | PEG 400 | PEG 600 | Ethylene glycol | Polyglycerol |
| Parts by weight | 0.5 | 5 | 2 | 4 | 4 | |
| Toughener | Substance | ___ | Aliphatic polyester | Aliphatic polyester | Aliphatic-ar omatic copolyester | Aliphatic-ar omatic copolyester |
| Parts by weight | 0 | 10 | 2 | 5 | 7 | |
| Processing aids | Substance | ___ | Oleic acid amide | PELESTAT -230 | Carbon black | Antioxidant |
| Parts by weight | 0 | 4 | 1 | 2 | 3 | |
| Impact strength / J/m | 58 | 77 | 65 | 73 | 63 | |
| Heat distortion temperature /°C | 88 | 96 | 107 | 111 | 92 |
It can be seen from Table 1 that the heat distortion temperature (HDT) of the polylactic acid
2019100618 08 Jun 2019 composite material of the present invention is not lower than 85 ° C, or even greater than or equal to 95 ° C, and the heat distortion temperature (HDT) of the polylactic acid composite material of the present invention under certain conditions. It may also be not lower than 106 ° C;
and, the polylactic acid composite material of the present invention has a notched impact strength of more than 54 J/m, and may even be higher than 70 J/m.
Example 6
The average size of the crystalline phase in the polylactic acid composite material of the present invention affects the properties of the polylactic acid composite material. To investigate the effect of the average size of the crystalline phase on the properties of the polylactic acid composite material, the applicant prepared the test group and the control according to the method of Example l.The polylactic acid composite material was assembled, and the properties of the polylactic acid composite material of the test group and the control group of the present example were tested in accordance with the test method for the properties of the polylactic acid composite material described in the above Example 1.
In the present embodiment, the composition and properties of the polylactic acid composite material of the test group and the control group are shown in Table 2.
Table 2
| Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 | Test group 6 | Test group 7 | Contr ol group 1 | Contr ol group 2 | ||
| Polylactic acid | Average size of crystal phase /pm | 0.99 | 0.90 | 0.8 | 0.75 | 0.68 | 0.50 | 0.45 | 1.0 | 1.1 |
| Percentage by weight of crystalline or semi-crystal line polylactic acid PLA 4032D in polylactic acid /% | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | |
| Percentage by weight of amorphous polylactic acid PLA 4060D in polylactic acid /% | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
2019100618 08 Jun 2019
| Parts by weight | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | |
| Talcum powder: TYT-8875 B | Parts by weight | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Average particle size D50/pm | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | |
| Calcium carbonate : 1T-CU | Parts by weight | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Average particle size D50/pm | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | |
| Plasticizer : PEG 600 | Parts by weight | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Impact strength / J/m | 56 | 58 | 61 | 63 | 67 | 72 | 73 | 52 | 49 | |
| Heat distortion temperature / °C | 87 | 90 | 95 | 97 | 106 | 108 | 108 | 85 | 83 |
In the above Table 2, the amorphous polylactic acid PLA 4060D, D-lactic acid content of 12%, purchased from NatureWorks; crystalline or semi-crystalline polylactic acid PLA4032D, L-lactic acid content of 98.5%, purchased from NatureWorks; Talc powder is TYT-8875B, the average particle size is 7~9pm, purchased from Haicheng Tianyuan Chemical Co., Ltd.; calcium carbonate is 1T-CU average particle size D50 is 1.8pm, purchased from Omya International AG; plasticizer is PEG 600, purchased at Hai'an Petrochemical Plant in Jiangsu Province.
It can be seen from Table 2 that in the polylactic acid composite material of the present invention, when the average particle diameter of the crystal phase is not more than 1.0 pm, the obtained polylactic acid composite material has remarkably improved notched impact strength and high heat distortion temperature; When the particle diameter is not more than 0.8 pm, the obtained polylactic acid composite material has better notched impact strength and heat distortion temperature performance; when the average particle diameter of the crystal phase is not more than 0.5 pm, the notched impact strength of the obtained polylactic acid composite material and The heat distortion temperature performance is the best.
At the same time, the applicant also investigated the average particle size of amorphous polylactic acid on the properties of polylactic acid composites when polylactic acid, talc, calcium carbonate and plasticizer were used as other substances and other parts by weight according to the above method. The effects are consistent with those shown in Table 2, and will not be repeated here.
Example 7
The content of the non-crystalline polylactic acid, the crystalline or semi-crystalline polylactic acid in the polylactic acid of the polylactic acid composite of the present invention affects the properties of the polylactic acid composite material, and the amorphous polylactic acid, crystalline or semi-crystalline polycondensation is investigated. The influence of the content of lactic acid on the properties of the polylactic acid composite material, the applicant prepared the test group and the control group polylactic acid composite material according to the method of
Example 1, and tested according to the test method of the performance of the polylactic acid composite material described in the above Example 1. The performance of the polylactic acid composite material of the test group and the control group of this example was as follows.
In the present embodiment, the composition and properties of the polylactic acid composite material of the test group and the control group are shown in Table 3.
2019100618 08 Jun 2019
Table 3
| Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 | Contr ol group 1 | Contr ol group 2 | Contr ol group 3 | Contr ol group 4 | ||
| Polylacti c acid | Average size of crystalline phase /pm | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.50 | 0.5 | 0.5 | 0.5 |
| Percentage by weight of crystalline or semi-crystal line polylactic acid PLA 4032D in polylactic acid /% | 95 | 65 | 80 | 75 | 85 | 98 | 100 | 50 | 0 | |
| Percentage by weight of amorphous polylactic acid PLA 4060D in polylactic acid /% | 5 | 35 | 20 | 25 | 15 | 2 | 0 | 50 | 100 | |
| Parts by weight | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | |
| Talcum powder: TYT-887 5B | Parts by weight | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Average particle size D50/pm | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | 7~9 | |
| Calcium | Parts by | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
2019100618 08 Jun 2019
| carbonat e: 1T-CU | weight | |||||||||
| Average particle size D50/pm | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | |
| Plasticiz er: PEG 600 | Parts by weight | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Impact strength / J/m | 62 | 67 | 72 | 71 | 70 | 45 | 40 | 48 | 50 | |
| Heat distortion temperature / °C | 100 | 96 | 108 | 106 | 107 | 110 | 113 | 52 | 50 |
In this embodiment, the types of polylactic acid, talc, calcium carbonate, plasticizer, and the purchaser are the same as in Example 6.
Comparing the control groups 2 and 4 in Table 3 with the test groups 1 to 5, it was found that the obtained polylactic acid composite material was excellent only when the crystalline or semi-crystalline polylactic acid and the non-crystalline polylactic acid were simultaneously present. Notched impact strength and heat distortion temperature performance. Further comparing each test group with the control group, it was found that in the polylactic acid, the weight percentage of the crystalline or semi-crystalline polylactic acid was 65% to 95%, and the weight percentage of the amorphous polylactic acid was 5% to 35%. The polylactic acid composite material has better notched impact strength and heat distortion temperature performance; when the weight percentage of the crystalline or semi-crystalline polylactic acid in the polylactic acid is 75% to 85%, the weight percentage of the amorphous polylactic acid is 15%. At ~25%, the obtained polylactic acid composite material is the most excellent in notched impact strength and heat distortion temperature performance.
At the same time, the applicant also examined polylactic acid, talc, calcium carbonate and plasticizer according to the above method, when other substances and other parts by weight of the invention, amorphous polylactic acid, crystalline or semi-crystalline polylactic acid The effect of the content of polylactic acid on the properties of the polylactic acid composite material is consistent with the results of Table 3, and will not be repeated here.
It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and are not intended to limit the scope of the present invention, although the present invention will be described in detail with reference to the preferred embodiments, The technical solutions of the present invention may be modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.
Claims (2)
1. A polylactic acid composite material comprising the following raw materials by weight: 55-80 parts of polylactic acid, 10~35 parts of talcum powder, 0~5 parts of calcium carbonate, 0~10 parts of toughening agent, 0 to 4 parts of the processing aid; wherein the polylactic acid is composed of (a) amorphous polylactic acid and (b) crystalline or semi-crystalline polylactic acid; an amorphous polylactic acid is used as the continuous phase, a crystalline or semi-crystalline polylactic acid is used as a crystal phase, and the average size of the crystal phase in the polylactic acid composite material is not more than 1 pm.
2. The polylactic acid composite material according to claim 1, wherein the average size of the crystal phase in the polylactic acid composite material is not more than 0.8 pm.
3. The polylactic acid composite material according to claim 2, wherein the average size of the crystal phase in the polylactic acid composite material is not more than 0.5 pm.
4. The polylactic acid composite according to claim 1, wherein the crystalline or semi-crystalline polylactic acid contains 95% by weight or more of L-lactic acid; and the amorphous polylactic acid contains 12% by weight or more of D-lactic acid.
5. The polylactic acid composite material according to any one of claims 1 to 4, wherein the polylactic acid has 65% to 95% of crystalline or semi-crystalline polylactic acid by weight, and 5% to 35% of the amorphous polylactic acid by weight.
6. The polylactic acid composite according to claim 5, wherein the polylactic acid has 75% to 85% of crystalline or semi-crystalline polylactic acid by weight, and 15% to 25% of the amorphous polylactic acid by weight.
7. The polylactic acid composite material according to claim 1, wherein at least one of the following (a) to (d) is:
(a) the talc powder has an average particle diameter D50 of 5 ~ 13 pm;
(b) the calcium carbonate has an average particle diameter D50 of 1 ~ 7 pm;
(c) the toughening agent is an aliphatic polyester or an aliphatic-aromatic copolyester;
(d) The processing aid is at least one of a mold release agent, a surfactant, a wax, an antistatic agent, a dye, a nucleating agent, and an antioxidant.
8. The polylactic acid composite material according to claim 1, further comprising a plasticizer, wherein the plasticizer is 0.5 to 5 parts by weight.
9. The polylactic acid composite according to claim 8, wherein the plasticizer is glycerin, polyglycerin, ethylene glycol, PEG-400, PEG-600, PEG-800, epoxidized soybean oil, At least one of citrate, acetyl citrate, triacetyl glyceride, dioctyl adipate.
10. The method for preparing a polylactic acid composite material according to any one of claims 1 to 9, comprising the steps of:
(1) Weighing the components other than talc in the polylactic acid composite material, mixing them uniformly, putting them into a twin-screw extruder, extruding and granulating to obtain a master batch;
(2) The masterbatch obtained in the step (1) is added to the twin-screw extruder in the manner of main feeding, and the talc powder is added into the twin-screw extruder in a side feeding manner, and extruded and granulated to obtain polylactic acid composite material.
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| AUPCT/CN2019/088761 | 2019-05-28 | ||
| PCT/CN2019/088761 WO2020034714A1 (en) | 2018-08-17 | 2019-05-28 | Polylactic acid composite material and preparation method therefor |
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| CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN112898750A (en) * | 2021-01-26 | 2021-06-04 | 嘉兴学院 | Full-biodegradable toughened polylactic acid composite material and preparation method thereof |
| CN114410094A (en) * | 2022-03-03 | 2022-04-29 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
| WO2022260613A1 (en) * | 2021-06-10 | 2022-12-15 | İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. | Production method of polylactite with efficient processability |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN111534066B (en) * | 2020-05-13 | 2022-07-05 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN112898750A (en) * | 2021-01-26 | 2021-06-04 | 嘉兴学院 | Full-biodegradable toughened polylactic acid composite material and preparation method thereof |
| WO2022260613A1 (en) * | 2021-06-10 | 2022-12-15 | İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. | Production method of polylactite with efficient processability |
| CN114410094A (en) * | 2022-03-03 | 2022-04-29 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
| CN114410094B (en) * | 2022-03-03 | 2024-03-19 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
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