CN104109363A - High-strength high-toughness transparent polylactic acid composition and preparation method thereof - Google Patents
High-strength high-toughness transparent polylactic acid composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength high-toughness transparent polylactic acid composition and a preparation method thereof. The high-strength high-toughness transparent polylactic acid composition is prepared from the following raw materials in parts by weight: 80-95 parts of levopolylactic acid, 5-20 parts of dextropolylactic acid, 0.05-1 part of antioxidant, 0.1-2 parts of solubilizer and 0-3 parts of other assistants. The polylactic acid composition prepared by the method provided by the invention has the characteristics of high tensile strength (68 MPa), high elongation at break (200%), high visible light transmittance (higher than 75%), favorable melting processibility, favorable heat resistance and the like. The mass percent of the polylactic acid in the composition is 95-99.8% above, and the composition is completely biodegradable. The preparation method is simple and environment-friendly, and can easily implement industrialization.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of bio-based and Biodegradable polymer material technical field, relate in particular to transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity and preparation method thereof.
Background technology
Poly(lactic acid) is that a kind of to take starch etc. be raw material, by fermentation, a kind of eco-friendly bio-based macromolecular material that obtains of the technique such as chemosynthesis.Produce and use procedure environmental protection, can not increase Greenhouse effect, after use, under physical environment or composting conditions, can be degraded to carbonic acid gas and water, can not damage environment.Therefore, along with the aggravation of the day by day in short supply and environmental pollution of petroleum resources, exploitation poly-lactic acid material substituting traditional petroleum base, non-degradable macromolecular material has important strategic importance.
Poly(lactic acid) (PLA) can be divided into three types according to its optically-active characteristic: Poly-L-lactic acid (PLLA), dextrorotation poly(lactic acid) (PDLA) and PDLLA (PDLLA).Because the poly(lactic acid) that optical purity is 100% is comparatively rare, in this patent, by D-lactic acid, being that the DL poly(lactic acid) of leading (> 95%) and containing a small amount of dextrolactic acid is called Poly-L-lactic acid, is that the DL poly(lactic acid) of leading (> 95%) and containing a small amount of D-lactic acid is called dextrorotation poly(lactic acid) by dextrolactic acid.Poly-L-lactic acid and dextrorotation poly(lactic acid) are all semi-crystalline polymer, its fusing point (170-180 ℃) and crystallinity have a difference with optical purity is different, after take D-lactic acid dextrolactic acid monomer content surpass 10% in main DL poly(lactic acid), poly(lactic acid) can lose crystallizing power, but (50/50, wt/wt) can form a kind of fusing point by intermolecular strong interaction is under certain condition the Stereocomplex poly(lactic acid) (sc-PLA) of 230 ℃ for Poly-L-lactic acid and dextrorotation poly(lactic acid).
Poly(lactic acid) has higher tensile strength (about 55～60MPa) and the excellent transparency (90% left and right), still also deposits snappiness poor (for example elongation at break little (2～6%) and the low (2～3kJ/m of notched Izod impact strength
2)), the defect such as crystallization is slow, heat-drawn wire is low, facile hydrolysis, had a strong impact on the Application Areas of poly(lactic acid).For widening the range of application of poly(lactic acid), the utmost point is necessary poly(lactic acid) to carry out modification.Publication number is that the Chinese invention patent of CN102924892A discloses a kind of dextrolactic acid and method with the copolymer toughened Poly-L-lactic acid of poly-dextrolactic acid of soft segment structural polymer composition of adopting, make its elongation at break reach 16%, its vicat softening temperature reaches 94 ℃ simultaneously, and tensile strength reaches 47MPa.Publication number is that the Chinese invention patent of CN101392093A makes the elongation at break of poly(lactic acid) bring up to 230% by add 5-40 part epichlorohydrin rubber in 100 parts of poly(lactic acid), but tensile strength is down to 36MPa simultaneously.In addition publication number is that the Chinese invention patent of CN101333332A, CN101875763A and CN103183937A discloses respectively the method that adopts acrylic acid esters co-polymer, MBS/softening agent, poly butylene succinate/egg-shell meal plasticizing polylactic acid.Although these toughner add the snappiness that can improve poly(lactic acid), sacrificed to a certain extent the tensile strength of poly(lactic acid), and resulting poly (lactic acid) composition is only that part biological base is or/and part biological degradation material.In addition, the introducing of incompatible polymer, due to the transparency of microphase-separated destructible poly(lactic acid).
The snappiness of poly(lactic acid) can also obtain by adding the method for softening agent.Publication number is that the Chinese invention patent of CN101983986A obtains the transparent polylactic resin of a kind of toughness by add the method for toughner and softening agent in poly(lactic acid).Publication number be the Chinese invention patent of CN101503565A by adding softening agent and nano silicon, oxidation inhibitor in poly(lactic acid), lubricant has obtained a kind of transparent biodegradable composite material.Although softening agent can improve the elongation at break (snappiness) of poly(lactic acid), significantly reduced tensile strength and the modulus of poly(lactic acid) simultaneously, and small molecules softening agent exists to defects such as the outside migrations of material.
The intensity of poly(lactic acid) can improve by adding the methods such as inorganic nano-particle, but puies forward high-intensity toughness and the transparency that simultaneously tends to damage poly-lactic acid material; The toughness of poly(lactic acid) can be achieved by adding elastic component, but tends to sacrifice intensity, modulus and the transparency of poly(lactic acid) when improving toughness.In addition, the thermotolerance of poly(lactic acid) can improve by adding rigidity ion/fiber and improving poly(lactic acid) degree of crystallinity, and this often also can sacrifice the transparency of poly(lactic acid), and makes it further embrittlement.Strength and modulus is high, toughness and good heat resistance, the good poly-lactic acid material of the transparency all have broad application prospects in fields such as expensive goods packing, logistics packaging, vegetable and fruit packaging, disposable product and even dutiable goods.Yet, there is no at present mature technology and can realize above-mentioned performance requriements simultaneously.Therefore, urgently develop a kind of new technology, improve the over-all properties of poly(lactic acid), to meet the need of market.
Summary of the invention
In view of this, the object of the invention is to propose the preparation method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity, to obtain the poly (lactic acid) composition that strength and modulus is high, snappiness good, transparency is high, melt-processable is good, poly(lactic acid) content is high, simultaneously composition fully biodegradable, and its preparation method is simple, environmental friendliness, easily realize industrialization.
Based on above-mentioned purpose, the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity provided by the invention is comprised of according to weight part proportioning separately following raw material: 80～95 parts of Poly-L-lactic acid, 5～20 parts of dextrorotation poly(lactic acid), 0.05～1 part, oxidation inhibitor, 0.1～2 part of expanding material, 0～2 part of other auxiliary agent.
Preferably, described Poly-L-lactic acid is a kind of semi-crystalline polymer, can obtain by lactic acid melt phase polycondensation, also can obtain by rac-Lactide ring-opening polymerization, and its left-handed optical purity is not less than 96%, and its weight-average molecular weight is 100,000～500,000 dalton.
Preferably, described dextrorotation poly(lactic acid) is also a kind of semi-crystalline polymer, can obtain by lactic acid melt phase polycondensation, also can obtain by rac-Lactide ring-opening polymerization, and its dextrorotation optical purity is not less than 96%, and its weight-average molecular weight is 20,000～200,000 dalton.
Part Poly-L-lactic acid and part dextrorotation poly(lactic acid) under certain condition original position form Stereocomplex poly(lactic acid), and are dispersedly to form in Poly-L-lactic acid matrix typical " sea-island " structure.Because consistency is good, there is molecular entanglement in interface in Stereocomplex poly(lactic acid) disperse phase and Poly-L-lactic acid matrix, gives interaction force stronger between disperse phase and matrix.
Alternatively, described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010, can stop or reduce the thermooxidative degradation of poly(lactic acid).
Preferably, described expanding material is at least one in the compound that contains two above epoxide groups.Epoxide group under shear at high temperature condition can with Poly-L-lactic acid and dextrorotation poly(lactic acid) macromole generation chemical bonding, reducing the molecular weight that in the course of processing, poly(lactic acid) degraded causes reduces, can original position form the segmented copolymer of Poly-L-lactic acid and dextrorotation poly(lactic acid), thereby improve consistency, the dispersion of optimizing above-mentioned Stereocomplex poly(lactic acid) and the distribution effect between Poly-L-lactic acid and Stereocomplex poly(lactic acid).The raising of poly(lactic acid) matrix molecular weight, itself can improve its snappiness.
Alternatively, described toughner can select business-like Bioadimide500XT (Lai Yin chemical company product), Bioadimide100 (Lai Yin chemical company product) and
at least one in (BASF AG's product).
Alternatively, the transparent poly (lactic acid) composition of above-mentioned a kind of high-intensity high-tenacity also can comprise other auxiliary agents, for example at least one in nucleator, processing aid, nanometer additive.The add-on of these auxiliary agents is little, can improve to a certain extent crystallization behavior, processing characteristics of said composition etc., but can obviously not affect mechanical property and the transparency of poly (lactic acid) composition.
The present invention also provides the preparation method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity, comprises the following steps:
First by dry Poly-L-lactic acid, dextrorotation poly(lactic acid), oxidation inhibitor, expanding material, other auxiliary agents according to weight part proportioning at room temperature premix evenly obtain mixture, then said mixture is obtained to the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity by Banbury mixer melt blending.Wherein said poly (lactic acid) composition is comprised of according to weight part proportioning separately following raw material: 80～95 parts of Poly-L-lactic acid, 5～20 parts of dextrorotation poly(lactic acid), 0.05～1 part, oxidation inhibitor, 0.1～2 part of expanding material, 0～2 part of other auxiliary agent.
Preferably, wherein Poly-L-lactic acid and dextrorotation poly(lactic acid) need to be fully dried before melt-processed, to reduce in melt-processed process because moisture exists poly(lactic acid) degraded and the performance cracking causing as far as possible.
Preferably, described Poly-L-lactic acid is a kind of semi-crystalline polymer, can obtain by lactic acid melt phase polycondensation or by rac-Lactide ring-opening polymerization, and its left-handed optical purity is not less than 96%, and its weight-average molecular weight is 100,000～500,000 dalton.
Preferably, described dextrorotation poly(lactic acid) is also a kind of semi-crystalline polymer, can obtain by lactic acid melt phase polycondensation or by rac-Lactide ring-opening polymerization, and its dextrorotation optical purity is not less than 96%, and its weight-average molecular weight is 20,000～200,000 dalton.
In melt blending process, part Poly-L-lactic acid and part dextrorotation poly(lactic acid) can original position under the effect of shearing force form Stereocomplex poly(lactic acid), and microphase-separated occurs, and are dispersedly to form in Poly-L-lactic acid matrix typical " sea-island " structure.There is molecular entanglement in interface in Stereocomplex poly(lactic acid) disperse phase and Poly-L-lactic acid matrix, gives good interaction force between disperse phase and matrix.
Original position forms and homodisperse Stereocomplex poly(lactic acid) both had enhancement to Poly-L-lactic acid matrix, as heterogeneous particles, in drawing process, can produce cavity and discharge local stress and strain, thereby make material change ductile rupture into by brittle rupture simultaneously.Larger (4～19) of Poly-L-lactic acid and dextrorotation poly(lactic acid) weight, make that formed Stereocomplex poly(lactic acid) particle diameter is little, content is moderate, thereby guarantee visible light transmittance rate that resulting poly (lactic acid) composition is higher and good melt-processable.
Preferably, described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010, can stop or reduce the thermooxidative degradation of poly(lactic acid) in melt blending and storage process.
Preferably, described expanding material is at least one in the compound that contains two above epoxide groups.Epoxide group on such expanding material under shear at high temperature condition can with a plurality of Poly-L-lactic acid and dextrorotation poly(lactic acid) macromole generation chemical bonding, not only poly(lactic acid) is had to chain extension and resistant to hydrolysis effect, reducing the molecular weight that in the course of processing, poly(lactic acid) degraded causes reduces, even can improve the molecular weight of poly(lactic acid), can also original position form the segmented copolymer of Poly-L-lactic acid and dextrorotation poly(lactic acid), thereby improve consistency, the dispersion of optimizing above-mentioned Stereocomplex poly(lactic acid) and the distribution effect between Poly-L-lactic acid and Stereocomplex poly(lactic acid).The raising of poly(lactic acid) matrix molecular weight, itself can improve its snappiness.
Alternatively, described toughner can select business-like Bioadimide500XT (Lai Yin chemical company product), Bioadimide100 (Lai Yin chemical company product) and
at least one in (BASF AG's product).
Alternatively, the transparent poly (lactic acid) composition of above-mentioned a kind of high-intensity high-tenacity also can comprise other auxiliary agents, for example at least one in nucleator, processing aid, nanometer additive.The add-on of these auxiliary agents is little, can improve to a certain extent crystallization behavior, processing characteristics of said composition etc., but can obviously not affect mechanical property and the transparency of poly (lactic acid) composition.
Alternatively, described melt blending temperature is 185～215 ℃, preferably 195～205 ℃.Stereocomplex poly(lactic acid) generally need to be below 240～250 ℃ melt-processable, result Thermal Degradation of Polylactic Acid is serious, and the Stereocomplex poly(lactic acid) percentage composition forming in the present invention is low, and for disperse phase is scattered in Poly-L-lactic acid matrix, therefore by the present invention, obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity is melt-processable under relatively lower temp, has effectively reduced the too high polylactic acid molecule chain degradation causing of melt processing temperature.
Alternatively, described closed-smelting machine rotor rotating speed is 30～150 revs/min, preferably 30～100 revs/min.
Alternatively, the described melt blending time is 3～10 minutes, preferably 5～7 minutes.
The transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity prepared in accordance with the present invention, through suitable moulding process or moulded products process simple thermal treatment, also can significantly improve its thermotolerance, improves poly (lactic acid) composition modulus at high temperature.
The present invention also provides the using method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity, described poly (lactic acid) composition can be by mold pressing, extrude, plastics that the forming method preparation such as injection moulding, blown film, calendering becomes different shape.
As can be seen from above, the preparation method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity provided by the invention can realize on conventional plastic processing units, and cost is low, environmental friendliness, easily realize industrialization.In the poly (lactic acid) composition obtaining according to preparation method provided by the invention, poly(lactic acid) content is up to more than 95%～99.8%, and strength and modulus is high, good toughness, the transparency are good.The forming method preparations such as described poly (lactic acid) composition can be by mold pressing, extrude, injection moulding, blown film, calendering become the plastics of different shape.By moulding process, regulate and control or simple thermal treatment also can significantly improve the thermotolerance of poly (lactic acid) composition.
It is emphasized that, the poly (lactic acid) composition relating in the present invention is not introduced the components such as any extra strengthening agent (as rigid filled), toughner (as elastomerics) and transparent base, but cleverly by technology such as regulation and control poly(lactic acid) self microtexture, microphase-separated, interface molecular interlocking, strain/stress induction matrix cavityizatioies, realized the self-enhancement of poly(lactic acid) and from toughness reinforcing simultaneously, and keep the good transparency, there is essential difference in this and the existing modification technology of poly(lactic acid).
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
First the vacuum-drying 8 hours at 80 ℃ of Poly-L-lactic acid and dextrorotation poly(lactic acid) is standby, then Poly-L-lactic acid 45g, dextrorotation poly(lactic acid) 5g, oxidation inhibitor (1010) 0.05g and expanding material (Bioadimide500XT) 0.5g premix is even, again by pre-composition at 200 ℃ by Banbury mixer melt blending 5 minutes (rotor speed is 30 revs/min), obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.In addition, sheet material is annealed 3 minutes under 100 ℃ of environment, then test the storage modulus before and after the thermal treatment of poly (lactic acid) composition sheet material under differing temps, test result is listed in table 2.
Embodiment 2
First the vacuum-drying 8 hours at 80 ℃ of Poly-L-lactic acid and dextrorotation poly(lactic acid) is standby, then Poly-L-lactic acid 40g, dextrorotation poly(lactic acid) 10g, oxidation inhibitor (1010) 0.1g, oxidation inhibitor (168) 0.02g and expanding material (Bioadimide500XT) 0.5g premix is even, again by pre-composition at 200 ℃ by Banbury mixer melt blending 6 minutes (rotor speed is 40 revs/min), obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.
Embodiment 3
First the vacuum-drying 8 hours at 80 ℃ of Poly-L-lactic acid and dextrorotation poly(lactic acid) is standby, then Poly-L-lactic acid 45g, dextrorotation poly(lactic acid) 5g, oxidation inhibitor (168) 0.05g and expanding material (Bioadimide500XT) 0.5g premix is even, again by pre-composition at 210 ℃ by Banbury mixer melt blending 5 minutes (rotor speed is 30 revs/min), obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.
Embodiment 4
First the vacuum-drying 8 hours at 80 ℃ of Poly-L-lactic acid and dextrorotation poly(lactic acid) is standby, then Poly-L-lactic acid 45g, dextrorotation poly(lactic acid) 5g, oxidation inhibitor (1010) 0.1g, oxidation inhibitor (168) 0.02g, expanding material (Bioadimide500XT) 0.6g and nucleator (TMC300) 0.25g premix is even, again by pre-composition at 200 ℃ by Banbury mixer melt blending 4 minutes (rotor speed is 50 revs/min), obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.
Embodiment 5
First the vacuum-drying 8 hours at 80 ℃ of Poly-L-lactic acid and dextrorotation poly(lactic acid) is standby, then by Poly-L-lactic acid 46g, dextrorotation poly(lactic acid) 4g, oxidation inhibitor (1010) 0.04g, expanding material (
) 0.5g, expanding material (Bioadimide100) 0.15g and nucleator (TMC300) 0.2g premix even, again by pre-composition at 195 ℃ by Banbury mixer melt blending 7 minutes (rotor speed is 50 revs/min), obtain the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.
Comparative example 1
First by the vacuum-drying 8 hours at 80 ℃ of 50g Poly-L-lactic acid, then at 200 ℃ by Banbury mixer melt blending 5 minutes (rotor speed is 30 revs/min), obtain a kind of transparent poly (lactic acid) composition.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.In addition, sheet material is annealed 3 minutes under 100 ℃ of environment, then test the storage modulus before and after the thermal treatment of poly (lactic acid) composition sheet material under differing temps, test result is listed in table 2.
Comparative example 2
First Poly-L-lactic acid and commercialization polylactic acid toughening modifier Biomax_strong120 vacuum-drying 8 hours at 80 ℃ is standby, then Poly-L-lactic acid 45 and Biomax_strong1205g premix is even, again by pre-composition at 200 ℃ by Banbury mixer melt blending 5 minutes (rotor speed is 30 revs/min), obtain a kind of poly (lactic acid) composition.Resulting poly (lactic acid) composition is hot-forming by vulcanizing press, obtain the plastics sheet of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing, optical performance test and thermal performance test according to relevant criterion, every test result is listed in table 1.
The performance perameter of poly (lactic acid) composition in table 1 embodiment and comparative example
Storage modulus under differing temps before and after poly (lactic acid) composition thermal treatment in table 2 embodiment and comparative example
It should be noted that, in above each embodiment and comparative example, Poly-L-lactic acid used is the product P LA4032D of U.S. NatureWorks LLC company, left-handed optical purity > 98%, and weight-average molecular weight is about 300,000 dalton.Dextrorotation poly(lactic acid) used is laboratory product (test grade), dextrorotation optical purity > 98%, and weight-average molecular weight is about 100,000 dalton.The Biomax_strong120 adopting in comparative example is E.I.Du Pont Company's product.Adopt expanding material Bioadimide500XT and Bioadimide100 Wei Lai mattress chemical company product, used
for BASF AG's product.Other chemical assistants are commercially available prod, and purity is more than 97%.
The step of the transparent poly (lactic acid) composition compacting of prepared a kind of high-intensity high-tenacity sheet material comprises: first the transparent poly (lactic acid) composition of prepared high-intensity high-tenacity is put into mould hot pressing on vulcanizing press (200 ℃ of hot pressing temperatures, 3 minutes warm up time, hot pressing time 2 minutes, hot pressing pressure 15MPa) cold pressing again to room temperature and (cold pressing 5 minutes time, pressure 15MPa colds pressing), make thickness and be the sheet material of 1 millimeter, for tensile property, thermal characteristics and visible light transmissivity test.
Wherein adopt electronic tensile test machine (Instron5967) at room temperature by the tensile property of standard GB/T/T528-2009 test sample, draw speed is 10 mm/min.Sample visible light transmissivity adopts twin-beam ultraviolet-visible pectrophotometer (TU-1901) to record the average transmittance in visible wavelength range, and sample thickness is 1.0 millimeters.Stereocomplex poly(lactic acid) melting enthalpy adopts PerkinElmer DSC8000 to record, and temperature rise rate is 10 ℃/min.It is to record under 100Hz condition at 200 ℃ with oscillation frequency that complex viscosity utilizes dull and stereotyped torque rheometer (TA Instruments, DHR-2).Under differing temps, the storage modulus of poly (lactic acid) composition sheet material records by DMA (TA Instrument, Q800), and Range of measuring temp is 20～150 ℃, and temperature rise rate is 3 ℃/min.
By embodiment, can be further illustrated, the advantages such as the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity obtaining by the present invention has biomass and biodegradable component concentration is high, strength and modulus is high, good toughness (elongation at break is large), the transparency good (visible light transmissivity is high), melt-processable good (at 200 ℃, melt viscosity is low), can meet the application demand in the fields such as expensive goods packing, logistics packaging, vegetable and fruit packaging, disposable product.Compare with Poly-L-lactic acid composition in comparative example 1, the tensile strength of the transparent poly (lactic acid) composition of high-intensity high-tenacity obtaining in embodiment 1～5 has improved 17%～24%, and Young's modulus has improved 7%～17%, and elongation at break has improved 21～40 times.With in comparative example 2, adopt special-purpose toughner (10wt%) polydactyl acid of commercialization poly(lactic acid) composition and compare, the tensile strength of the transparent poly (lactic acid) composition of high-intensity high-tenacity obtaining in embodiment 1～5 has improved 70%～80%, Young's modulus has improved 24%～36%, and visible light transmissivity improves 64～75 times.
The storage modulus under 3 minutes front and back differing tempss of thermal treatment at 100 ℃ by embodiment and comparative example, can further illustrate by the transparent poly (lactic acid) composition of the prepared a kind of high-intensity high-tenacity of the present invention and pass through simple thermal treatment (80～100 ℃) maintenance high modulus under comparatively high temps afterwards.Compare with comparative example 1 before and after thermal treatment, the modulus of the embodiment 1 after thermal treatment at 100 ℃ improves respectively 10 times and 2 times; Compare with the embodiment 1 before thermal treatment, the modulus of the embodiment 4 after thermal treatment at 100 ℃ improves approximately 1 times.
Visible, content of the present invention is to the polylactic acid modified technology of tradition breakthrough, can obtain high strength, high-modulus and the transparency simultaneously.The complex viscosity of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity provided by the invention under high frequency is lower, can be directly on conventional plastic processing units for mold pressing, extrude, plastics that the forming method preparation such as injection moulding, blown film, calendering becomes different shape, cost is low, environmental friendliness, easily realize industrialization, through simple thermal treatment, can also significantly improve the thermotolerance of corresponding plastics, widen its temperature limit.
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the transparent poly (lactic acid) composition of high-intensity high-tenacity, is characterized in that, consists of: 80～95 parts of Poly-L-lactic acid following raw material according to weight part proportioning separately, 5～20 parts of dextrorotation poly(lactic acid), 0.05～1 part, oxidation inhibitor, 0.1～2 part of expanding material, 0～2 part of other auxiliary agent.
2. the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity according to claim 1, is characterized in that, in described Poly-L-lactic acid, left-handed optical purity is not less than 96%, and weight-average molecular weight is 100,000～500,000 dalton.
3. the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity according to claim 1, is characterized in that, in described dextrorotation poly(lactic acid), dextrorotation optical purity is not less than 96%, and weight-average molecular weight is 20,000～200,000 dalton.
4. the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity according to claim 1, is characterized in that, described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010.
5. the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity according to claim 1, is characterized in that, described expanding material is at least one in the compound that contains two above epoxide groups.
6. the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity according to claim 1, is characterized in that, described other auxiliary agents are at least one in nucleator, processing aid, nanometer additive.
7. a preparation method for the transparent poly (lactic acid) composition of high-intensity high-tenacity, is characterized in that, said method comprising the steps of:
First by dry Poly-L-lactic acid, dextrorotation poly(lactic acid), oxidation inhibitor, expanding material, other auxiliary agents according to weight part proportioning at room temperature premix evenly obtain mixture, then said mixture is obtained to the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity by Banbury mixer melt blending.
8. according to the preparation method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity described in claim 7, it is characterized in that, described poly (lactic acid) composition is comprised of according to weight part proportioning separately following raw material: 80～95 parts of Poly-L-lactic acid, 5～20 parts of dextrorotation poly(lactic acid), 0.05～1 part, oxidation inhibitor, 0.1～2 part of expanding material, 0～2 part of other auxiliary agent, wherein
In described Poly-L-lactic acid, left-handed optical purity is not less than 96%, and weight-average molecular weight is 100,000～500,000 dalton;
In described dextrorotation poly(lactic acid), dextrorotation optical purity is not less than 96%, and weight-average molecular weight is 20,000～200,000 dalton;
Described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010;
Described expanding material is at least one in the compound that contains two above epoxide groups;
Described other auxiliary agents are at least one in nucleator, processing aid, nanometer additive.
9. according to the preparation method of the transparent poly (lactic acid) composition of a kind of high-intensity high-tenacity described in claim 7, it is characterized in that, described melt blending temperature is 185～215 ℃, and the melt blending time is 3～10 minutes, and closed-smelting machine rotor rotating speed is 30～150 revs/min.
10. according to the transparent poly (lactic acid) composition of any one described a kind of high-intensity high-tenacity in claim 1～9, it is characterized in that, the plastics of the method moulding different shapes such as described poly (lactic acid) composition can be by mold pressing, extrude, injection moulding, blown film, calendering, described plastics can significantly improve its thermotolerance after simple thermal treatment.
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| CN105038158A (en) * | 2015-07-24 | 2015-11-11 | 常州大学 | Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material |
| CN105936742A (en) * | 2016-06-07 | 2016-09-14 | 常州大学 | Preparation method of low-cost heat-resistant food grade polylactic acid material |
| CN106280335A (en) * | 2016-08-25 | 2017-01-04 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material of a kind of easy coloring and dyeing thereof |
| CN106349667A (en) * | 2016-08-31 | 2017-01-25 | 深圳市虹彩新材料科技有限公司 | High strength and high heat resistance polylactic acid composite material and preparation method thereof |
| CN106366594A (en) * | 2016-08-30 | 2017-02-01 | 江西师范大学 | Preparation method of high-toughness polylactic acid blend containing polylactic acid stereo compound |
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| CN105038158A (en) * | 2015-07-24 | 2015-11-11 | 常州大学 | Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material |
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| CN106366594B (en) * | 2016-08-30 | 2020-04-17 | 江西师范大学 | Preparation method of high-toughness polylactic acid blend containing polylactic acid stereo compound |
| CN106366594A (en) * | 2016-08-30 | 2017-02-01 | 江西师范大学 | Preparation method of high-toughness polylactic acid blend containing polylactic acid stereo compound |
| CN106349667A (en) * | 2016-08-31 | 2017-01-25 | 深圳市虹彩新材料科技有限公司 | High strength and high heat resistance polylactic acid composite material and preparation method thereof |
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| CN111944285A (en) * | 2020-08-07 | 2020-11-17 | 广州华新科智造技术有限公司 | Polylactic acid composition, toughened transparent material and preparation method thereof |
| CN112592567A (en) * | 2020-12-11 | 2021-04-02 | 金旸（厦门）新材料科技有限公司 | Full-biodegradable material containing superfine stereo composite polylactic acid |
| CN115322525A (en) * | 2022-10-11 | 2022-11-11 | 南通佰凯吉包装科技有限公司 | Multilayer composite transparent packaging bag and production process thereof |
| CN115746642A (en) * | 2022-11-29 | 2023-03-07 | 广东美涂士建材股份有限公司 | Antiviral antibacterial environment-friendly nano coating and preparation method thereof |
| CN115746642B (en) * | 2022-11-29 | 2024-04-05 | 广东美涂士建材股份有限公司 | Antiviral antibacterial environment-friendly nano coating and preparation method thereof |
| CN116200019A (en) * | 2023-01-17 | 2023-06-02 | 湖北鑫丰生态科技有限公司 | Degradable mulching film and preparation method thereof |
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