CN104592723A - Rapid-crystallization polylactic acid plastic and preparation method thereof - Google Patents
Rapid-crystallization polylactic acid plastic and preparation method thereof Download PDFInfo
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- CN104592723A CN104592723A CN201410605786.XA CN201410605786A CN104592723A CN 104592723 A CN104592723 A CN 104592723A CN 201410605786 A CN201410605786 A CN 201410605786A CN 104592723 A CN104592723 A CN 104592723A
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Abstract
The invention discloses a rapid-crystallization polylactic acid composite material and a preparation method thereof. The rapid-crystallization polylactic acid composite material comprises, by mass, 86-99.79% of polylactic acid, 0.1-10% of a high-molecular ion polymer, 0.01-2% of an anti-oxidant and 0.1-2% of a lubricant. The preparation method comprises the following steps of blending the above raw materials, carrying out injection, carrying molding, and carrying out blow molding to obtain the rapid-crystallization polylactic acid plastic. The blending process is a melt blending extrusion granulation method and a blending temperature is in a range of 140-240 DEG C. Compared with the prior art, the preparation method has the advantages that 1, a chemically reactive nucleating agent produces nucleating effects at the molecular level, a crystallization speed is fast, an injection molding period is shortened and processing efficiency is improved, and 2, an organic polymer nucleating agent has good compatibility with polylactic acid and is not separated easily so that adverse influence on product appearance is reduced.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of fast crystallization type polylactic acid composite material, and utilize macroion polymkeric substance as nucleating agent in polylactic acid production to prepare the method for fast crystallization type polylactic acid composite material.
Background technology
Along with the arriving in biodegradable plastic epoch, poly(lactic acid) is no matter from research and development with produce, or the aspect such as application has all established its first kind status in biodegradable plastic field.
Although poly(lactic acid) has achieved industrialization and produced, in its evolution, still there is a series of technical problem has needed to go into overdrive to tackle key problems.As crystallization rate is slow, heat-drawn wire is low, and shock resistance is poor, too expensive etc.In recent years, along with deepening continuously of poly(lactic acid) research, poly(lactic acid) Problems existing such as the problems such as production prices, shock resistance, thermotolerance have made moderate progress and have improved, but the crystallization rate of poly(lactic acid) is slow, the problem that degree of crystallinity is low is not really solved, and the production efficiency that especially polylactic acid crystal speed is brought slowly lowly remains problem the most urgent in poly(lactic acid) industry development.For this reason, researchist promotes the crystallization rate of poly(lactic acid) by various means.
Current raising polylactic acid crystal speed mainly contains four kinds of ways: add crystallization nucleating agent; Softening agent; The left-handed degree of adjustment polylactic acid molecule; Change condition of molding, especially mold temperature and molding time.
Add softening agent to increase to polylactic acid crystal performance, but effect not obvious, and a large amount of uses of this external plasticizer also can increase the production cost of poly(lactic acid); The poly(lactic acid) obtaining high left-handed degree in building-up process must have single-minded catalyzer and the synthesis technique of complexity, and production cost is very high; And when injection molding by setting higher die temperature, extending the crystal property improving poly(lactic acid) cooling time, energy consumption can be increased undoubtedly, extend shaping cycle, be unfavorable for High-efficient Production.Therefore, adding crystallization nucleating agent is improve the most feasible industrial method of polylactic acid crystal speed.
Nucleator is exist as the nucleus of poly(lactic acid) in polylactic acid crystal process, promotes crystal growth, reaches the object improving polylactic acid crystal speed.Mineral compound is used as polylactic acid crystal nucleator the earliest, and up till now, mineral-type crystallization nucleating agent mainly contains laminar silicate compounds as talcum powder, kaolin, polynite, mica etc.; Inorganic salts compound is as calcium lactate, basic mineral aluminum compound, calcium carbonate, barium sulfate etc.; Inorganic non-metallic type oxide is as silicon-dioxide, titanium dioxide etc.; Carbon material is as carbon black, carbon nanotube, soccerballene etc., and wherein talcum powder, polynite, carbon nanotube are the most frequently used polylactic acid crystal nucleators, and the inorganic nano material such as silicon-dioxide, calcium carbonate also has certain nucleogenesis to poly(lactic acid).The development that mineral compound is used as polylactic acid crystal nucleator is existing for many years, and its research also achieves certain breakthrough.But, over all, existing mineral-type nucleator is also difficult to the requirement meeting suitability for industrialized production, the flexible chain of poly(lactic acid) significantly can be shortened although add a large amount of inorganic nucleators, but the mechanical property of material is also lost substantially, loses using value.In addition, due to the poor compatibility of mineral compound and poly(lactic acid), it all needs to carry out functionalization reprocessing to inorganic nucleator before use substantially, and this has run counter to inorganic nucleator original intention with low cost undoubtedly; In addition, the structure designability of inorganic nucleator is poor, and the mechanism of nucleation of inorganic nucleator is indefinite, adds larger difficulty for designing and developing novel inorganic nucleator further.
Compare inorganic nucleator, the consistency of organic nucleating agent and poly(lactic acid) obtains very big improvement, and the nucleating effect of organic nucleating agent is also very remarkable.The most important thing is, the molecular structure of poly(lactic acid) be familiar with by the mankind after, researchist can the organic nucleating agent of experimentally result design and synthesizing new.Also just based on this, as Sorbitol Powder compounds, Metal organophosphates compound, M-nitro benzoic acid salt compound, ethylene bis stearic acid amide, nucite, pyrocatechol, hydroquinone two hydroxy ethyl ether, 4, the organic compound such as 4 '-dihydroxydiphenyl methane, 1, 4-benzenediol, cage type ammonia chloride propyl group polysilsesquioxane, polyhedral oligomeric silsesquioxane are screened or be synthesized as the crystallization nucleating agent of poly(lactic acid).US Patent No. 6417294 is by adding the composite nucleating agents such as aliphatic carboxylic acid amine, aliphatic carboxylate, fatty alcohol and aliphatic carboxylic acid fat in poly(lactic acid) matrix, acquisition has the transparency and crystalline poly-lactic acid products, but these small molecules organic nucleating agents are easily overflowed after making masterbatch or product with poly(lactic acid), thus cause actual nucleator addition to reduce, nucleating effect reduces, and affects products appearance and use properties.
Summary of the invention
The object of the invention is to provide a kind of fast crystallization type polylactic acid composite material, solving the problems referred to above of prior art.
Another object of the present invention is to provide the preparation method of above-mentioned matrix material.
The object of the invention is to be achieved through the following technical solutions.
A kind of fast crystallization type polylactic acid composite material, is made up of the raw material of following mass percent:
The mass percent sum of each component is 100% above.
Wherein, the weight-average molecular weight of described poly(lactic acid) is 50000 ~ 500000, the preferably poly(lactic acid) of 100000 ~ 200000; In above-mentioned poly(lactic acid), the formation mol ratio (L/D) of Pfansteihl unit and D-ALPHA-Hydroxypropionic acid unit is less than 1, and the molar content of preferred D-ALPHA-Hydroxypropionic acid unit answers the poly(lactic acid) of more than 75%.
Described macroion polymkeric substance is the macroion polymkeric substance containing sodium Metal 99.5 ion in molecule.
Described oxidation inhibitor is one or both in the mixture (irgasfos 168) of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
Described lubricant is ethylene bis stearamide (EBS).
Prepare a method for above-mentioned rapid crystallization polylactic acid plastics, comprise the following steps:
Take poly(lactic acid), macroion polymkeric substance, oxidation inhibitor, lubricant is blended according to the above ratio, then injects, mold pressing, and blowing etc. are shaping obtains rapid crystallization polylactic acid plastics; Wherein, described blend method is melt blending extruding pelletization method; Described blending temperature is 140 DEG C-240 DEG C.
The present invention adopts macroion polymkeric substance as the crystallization nucleating agent of poly(lactic acid); Macroion polymkeric substance can accelerate the crystallization of PLA, PLA and macroion polymkeric substance generation chemical reaction generate the polymer with ionic end groups as PLA-COONa, this ionic end groups segregation in the melt, forms out-phase microcell, serves nucleogenesis.These ionic end groups form ion cluster by electrostatic forcing simultaneously, also can become heterogeneous nucleation center, thus improve PLA nucleation rate at high temperature, promote crystallization.
Macroion polymkeric substance is because be polymer, and molecular weight is large, and is polar material, has good consistency with the poly(lactic acid) being all organic high molecular polymer, avoids the problem that low molecule organic matter or inorganics nucleator are easily separated out.
Compared with prior art, the present invention has following beneficial effect:
1, chemical reactivity nucleator, molecular level plays nucleogenesis, and crystallization velocity is fast, shortens injection cycle, improves working (machining) efficiency;
2, organic polymer class nucleator, good with poly(lactic acid) consistency, be not easy to separate out, reduce the detrimentally affect to product appearance.
Embodiment
Technical characterstic of the present invention is set forth further below in conjunction with specific embodiment.
Comparative example: weigh 2970 grams of poly(lactic acid) (weight-average molecular weight 180000), 5 grams of antioxidant 1010s, 11 grams of irgasfos 168s and 15 grams of Lubricate EBSs, extruding pelletization on Small-size Twin-Screw Extruders forcing machine, makes lactic acid composite material.By poly-lactic acid material differential calorimetric scan instrument (DSC) obtained under nitrogen atmosphere 190 DEG C of heating poly(lactic acid) was melted in 5 minutes, then with the speed of 2 DEG C/min by melt cooling measure this polylactic acid crystal peak temperature for Tc., and the hypocrystalline temperature t changing material is calculated by dependent equation
1/2.Tc value is higher, t
1/2less crystallization rate is faster, and the machine-shaping cycle is shorter.
Embodiment 1: weigh 2955 grams of poly(lactic acid) (weight-average molecular weight 180000), 15 grams of macroion polymkeric substance Du Pont sarins
the trade mark 8920,5 grams of antioxidant 1010s, 11 grams of irgasfos 168s and 15 grams of Lubricate EBSs, extruding pelletization on Small-size Twin-Screw Extruders forcing machine, makes lactic acid composite material.By poly-lactic acid material differential calorimetric scan instrument (DSC) obtained under nitrogen atmosphere 190 DEG C of heating poly(lactic acid) was melted in 5 minutes, then with the speed of 2 DEG C/min by melt cooling measure this polylactic acid crystal peak temperature for Tc., and the hypocrystalline temperature t changing material is calculated by dependent equation
1/2.Tc value is higher, t
1/2less crystallization rate is faster, and the machine-shaping cycle is shorter.
Embodiment 2: weigh 2940 grams of poly(lactic acid) (weight-average molecular weight 180000), 30 grams of macroion polymkeric substance Du Pont sarins
the trade mark 8920,5 grams of antioxidant 1010s, 11 grams of irgasfos 168s and 15 grams of Lubricate EBSs, extruding pelletization on Small-size Twin-Screw Extruders forcing machine, makes lactic acid composite material.By poly-lactic acid material differential calorimetric scan instrument (DSC) obtained under nitrogen atmosphere 190 DEG C of heating poly(lactic acid) was melted in 5 minutes, then with the speed of 2 DEG C/min by melt cooling measure this polylactic acid crystal peak temperature for Tc., and the hypocrystalline temperature t changing material is calculated by dependent equation
1/2.Tc value is higher, t
1/2less crystallization rate is faster, and the machine-shaping cycle is shorter.
Embodiment 3: weigh 2880 grams of poly(lactic acid) (weight-average molecular weight 180000), 90 grams of macroion polymkeric substance Du Pont sarins
the trade mark 8920,5 grams of antioxidant 1010s, 11 grams of irgasfos 168s and 15 grams of Lubricate EBSs, extruding pelletization on Small-size Twin-Screw Extruders forcing machine, makes lactic acid composite material.By poly-lactic acid material differential calorimetric scan instrument (DSC) obtained under nitrogen atmosphere 190 DEG C of heating poly(lactic acid) was melted in 5 minutes, then with the speed of 2 DEG C/min by melt cooling measure this polylactic acid crystal peak temperature for Tc., and the hypocrystalline temperature t changing material is calculated by dependent equation
1/2.Tc value is higher, t
1/2less crystallization rate is faster, and the machine-shaping cycle is shorter.
Embodiment 4: weigh 2670 grams of poly(lactic acid) (weight-average molecular weight 180000), 300 grams of macroion polymkeric substance Du Pont sarins
the trade mark 8920,5 grams of antioxidant 1010s, 11 grams of irgasfos 168s and 15 grams of Lubricate EBSs, extruding pelletization on Small-size Twin-Screw Extruders forcing machine, makes lactic acid composite material.By poly-lactic acid material differential calorimetric scan instrument (DSC) obtained under nitrogen atmosphere 190 DEG C of heating poly(lactic acid) was melted in 5 minutes, then with the speed of 2 DEG C/min by melt cooling measure this polylactic acid crystal peak temperature for Tc., and the hypocrystalline temperature t changing material is calculated by dependent equation
1/2.Tc value is higher, t
1/2less crystallization rate is faster, and the machine-shaping cycle is shorter.
Table 1 is the component of embodiment 1-4 and comparative example and respective material Tc thereof and flexible chain test data:
As can be seen from the data of table 1, after embodiment 1-4 employs the macroion polymkeric substance of certain mass percent relative to comparative example, Tc is high, and crystallization velocity is fast, substantially reduces injection cycle, improves working (machining) efficiency.
Claims (9)
1. a fast crystallization type polylactic acid composite material, is characterized in that: be made up of the raw material of following mass percent:
The mass percent sum of each component is 100% above.
2. fast crystallization type polylactic acid composite material according to claim 1, is characterized in that: the weight-average molecular weight of described poly(lactic acid) is 50000 ~ 500000.
3. fast crystallization type polylactic acid composite material according to claim 2, is characterized in that: the weight-average molecular weight of described poly(lactic acid) is 100000 ~ 200000.
4. fast crystallization type polylactic acid composite material according to claim 1, is characterized in that: in described poly(lactic acid), and the formation mol ratio (L/D) of Pfansteihl unit and D-ALPHA-Hydroxypropionic acid unit is less than 1.
5. fast crystallization type polylactic acid composite material according to claim 4, is characterized in that: in described poly(lactic acid), and the molar content of D-ALPHA-Hydroxypropionic acid unit answers more than 75%.
6. fast crystallization type polylactic acid composite material according to claim 1, is characterized in that: described macroion polymkeric substance is the macroion polymkeric substance containing sodium Metal 99.5 ion in molecule.
7. fast crystallization type polylactic acid composite material according to claim 1, it is characterized in that: described oxidation inhibitor is one or both in the mixture of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
8. fast crystallization type polylactic acid composite material according to claim 1, is characterized in that: described lubricant is ethylene bis stearamide (EBS).
9. prepare a method for rapid crystallization polylactic acid plastics described in claim 1, it is characterized in that: comprise the following steps:
Take poly(lactic acid), macroion polymkeric substance, oxidation inhibitor, lubricant is blended according to the above ratio, then injects, mold pressing, and blowing etc. are shaping obtains rapid crystallization polylactic acid plastics; Wherein, described blend method is melt blending extruding pelletization method; Described blending temperature is 140 DEG C-240 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110016133A (en) * | 2019-04-26 | 2019-07-16 | 安徽农业大学 | A kind of macromole nucleating agent and its application method for quickly crystallizing polylactic acid |
| CN112876826A (en) * | 2021-01-18 | 2021-06-01 | 山东科技大学 | Method for promoting polylactic acid stereo composite crystallization |
| CN115806732A (en) * | 2022-12-14 | 2023-03-17 | 普立思生物科技有限公司 | Quick-crystallization polylactic acid material and preparation method thereof |
| CN116355373A (en) * | 2023-04-20 | 2023-06-30 | 四川大学 | Polylactic acid-based composite material and preparation method thereof |
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| CN101235192A (en) * | 2007-02-02 | 2008-08-06 | 东丽纤维研究所（中国）有限公司 | Polylactic acid and plant fiber composite material and preparation method thereof |
| CN102002222A (en) * | 2010-10-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant polylactic acid composite material |
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Patent Citations (4)
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| US20050123744A1 (en) * | 2002-11-26 | 2005-06-09 | Mohanty Amar K. | Environmentally friendly polylactide-based composite formulations |
| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN101235192A (en) * | 2007-02-02 | 2008-08-06 | 东丽纤维研究所（中国）有限公司 | Polylactic acid and plant fiber composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016133A (en) * | 2019-04-26 | 2019-07-16 | 安徽农业大学 | A kind of macromole nucleating agent and its application method for quickly crystallizing polylactic acid |
| CN110016133B (en) * | 2019-04-26 | 2021-10-26 | 安徽农业大学 | Macromolecular nucleating agent for rapid crystallization of polylactic acid and use method thereof |
| CN112876826A (en) * | 2021-01-18 | 2021-06-01 | 山东科技大学 | Method for promoting polylactic acid stereo composite crystallization |
| CN115806732A (en) * | 2022-12-14 | 2023-03-17 | 普立思生物科技有限公司 | Quick-crystallization polylactic acid material and preparation method thereof |
| CN116355373A (en) * | 2023-04-20 | 2023-06-30 | 四川大学 | Polylactic acid-based composite material and preparation method thereof |
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