CN102040815A - Method for plasticizing and modifying polylactic acid - Google Patents
Method for plasticizing and modifying polylactic acid Download PDFInfo
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- CN102040815A CN102040815A CN 201010618280 CN201010618280A CN102040815A CN 102040815 A CN102040815 A CN 102040815A CN 201010618280 CN201010618280 CN 201010618280 CN 201010618280 A CN201010618280 A CN 201010618280A CN 102040815 A CN102040815 A CN 102040815A
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Abstract
The invention discloses a method for plasticizing and modifying polylactic acid, and relates to the technical field of high molecular materials. Plasticization and modification are realized by blending, banburying and molding the polylactic acid, tirbutyl citrate and cyclohexane-1,2-dicarboxylic diisononyl ester. The method has the advantages of improving the breaking elongation and the impact strength of a material, along with simple steps and high applicability.
Description
Technical field
What the present invention relates to is a kind of method of technical field of polymer materials, specifically is a kind of plasticization and modification method of poly(lactic acid).
Background technology
Poly(lactic acid) (PLLA) can be applied to bio-medical field and packaging field.The second-order transition temperature of PLLA is 55-65 ℃, if be used for soft material, Tg is higher.Be lower than under the Tg temperature, PLLA is in vitreous state, and when temperature was higher than Tg, PLLA presented bigger rebound resilience, snappiness and shock strength.Plasticization and modification PLLA is the effective ways that improve the PLLA mechanical property.The softening agent that is used for the PLLA plasticization and modification is required to be nontoxic, environment-friendly type softening agent, thereby can satisfy application such as bio-medical, food product pack and environmental protection better.
Find that through retrieval Chinese patent CN1687233 discloses the method with TBC plasticization and modification poly(lactic acid), but TBC there is stronger transport property in material, be unfavorable for the permanent use of material to prior art; Chinese patent CN 1857235 discloses a kind of and Reoplex replaces the small molecules softening agent to come poly(lactic acid) is carried out plasticization and modification, solved small molecules migration of plasticizer problem, but raising has only about 1.5 times to the poly(lactic acid) elongation at break, the preparation method of this polymeric plasticizer is comparatively complicated simultaneously, is unfavorable for suitability for industrialized production; Polymer Engineering and Science has reported the method that single use TBC and DINCH come PLLA is carried out plasticization and modification at 2009 the 49th volume 2414-2420 pages or leaves, when only adding 10 parts of DINCH to PLLA, elongation at break can reach 129%, the elongation at break that is used alone the material that softening agent obtains is big not enough, often can not reach the performance requriements of high-performance occasion.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of plasticization and modification method of poly(lactic acid) is provided, the implementation method step is simple in elongation at break that strengthens material and shock strength, the advantage that suitability is strong.
The present invention is achieved by the following technical solutions, and the present invention is by with poly(lactic acid), tributyl citrate with as the hexanaphthene-1 of softening agent, and moulded section after the 2-dicarboxyl dinonyl blend banburying realizes plasticization and modification.
Described poly(lactic acid), tributyl citrate and hexanaphthene-1, the part by weight of 2-dicarboxyl dinonyl is 100: 5-20: 5-20.
The melting index of described poly(lactic acid) be (190 ℃, 2.16kg) 5-12g/10min, promptly at 190 ℃, under the load of 2.16kg, the melt of poly(lactic acid) is by a diameter 2.1mm pipe, effusive quality is 5-12g.
Described poly(lactic acid) places 70 ℃ of dry 10h of vacuum drying oven in advance.
Described blend banburying is meant: under 160-170 ℃ blending temperature, add poly(lactic acid), tributyl citrate and hexanaphthene-1 successively, 2-dicarboxyl dinonyl and with the mixing 7-15 of 30-80 rpm speed minute.
Described moulded section is meant: insert in the mould after the material cooled with the blend banburying, carried out hot pressing in 1-5 minute successively and colded pressing in 10-30 minute after 160-170 ℃ of following preheating 2-5 minute, pressure is 13-18MPa.
The present invention has adopted plasticizer tirbutyl citrate and plasticizer cyclohexane alkane-1, the method of 2-dicarboxyl dinonyl and usefulness, utilize softening agent to reduce the second-order transition temperature of poly(lactic acid), improve the elongation at break and the shock strength of material, make material have high strength, the characteristics of high tenacity, at hexanaphthene-1,2-dicarboxyl dinonyl add-on is 15 parts, when the tributyl citrate add-on is 5 parts, elongation at break reaches 325%, and shock strength reaches 149J/m, satisfies the demand in packing and bio-medical field.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Following examples material therefor is: poly(lactic acid): trade mark 3051D, melting index (190 ℃, 2.16kg) 10g/10min, U.S. Natureworks company product.
Embodiment
The embodiment of the invention may further comprise the steps:
Before the first step, the blend, poly(lactic acid) is placed 70 ℃ of dry 10h of vacuum drying oven;
Second step, poly(lactic acid) and softening agent with drying after good are pre-mixed evenly in table 1 ratio, then melt blending in German Haake RC90 torque rheometer.Blending temperature is 170 ℃, and rotating speed is 50 rpms, and the blend time is 10min;
The 3rd step, the gained sample is placed mould, in 170 ℃ of following preheating 3min, hot pressing 2min under 15MPa then, the 15min moulding of colding pressing again, pressure is 15MPa, presses the sample preparation of ASTM standard, and material is carried out performance test.
Comparative example 1
Do not add softening agent in the prescription, complete processing is with embodiment 1-5.
Table 1 embodiment and Comparative Examples prescription (unit is a weight part)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples | |
| Poly(lactic acid) | 100 | 100 | 100 | 100 | 100 | 100 |
| Tributyl citrate | 5 | 5 | 10 | 10 | 15 | 0 |
| Hexanaphthene-1,2-dicarboxyl dinonyl | 5 | 10 | 5 | 10 | 5 | 0 |
Table 2 thickness of sample is 1.0mm, the mechanical property result during rate of extension 20mm/min
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples | |
| Tensile strength (MPa) | 41.5 | 24.6 | 35.8 | 31.9 | 27.3 | 69.5 |
| Elongation at break (%) | 6 | 143 | 309 | 325 | 175 | 4 |
| Notched Izod impact strength (J/m) | 37 | 72 | 40 | 72 | 149 | 29 |
As can be seen from Table 2, adopt present method to add plastic binder tributyl citrate and hexanaphthene-1,2-dicarboxyl dinonyl plasticized poly lactic acid, when the adding softening agent respectively is 5 parts (embodiment 1), the material toughening effect is not obvious, along with the softening agent add-on increases, the elongation at break of material and notched Izod impact strength all have significantly raising, especially elongation at break has improved at most about 80 times, and notched Izod impact strength has at most also improved more than 500%.Plastic binder tributyl citrate and hexanaphthene-1,2-dicarboxyl dinonyl has improved the toughness of poly(lactic acid).
Claims (6)
1. the plasticization and modification method of a poly(lactic acid) is characterized in that, by with poly(lactic acid), tributyl citrate with as the hexanaphthene-1 of softening agent, moulded section after the 2-dicarboxyl dinonyl blend banburying realizes plasticization and modification.
2. the plasticization and modification method of poly(lactic acid) according to claim 1 is characterized in that, described poly(lactic acid) places 70 ℃ of dry 10h of vacuum drying oven in advance.
3. the plasticization and modification method of poly(lactic acid) according to claim 1, it is characterized in that, described blend banburying is meant: under 160-170 ℃ blending temperature, add poly(lactic acid), tributyl citrate and hexanaphthene-1 successively, 2-dicarboxyl dinonyl and with the mixing 7-15 of 30-80 rpm speed minute.
4. the plasticization and modification method of poly(lactic acid) according to claim 1, it is characterized in that, described moulded section is meant: insert in the mould after the material cooled with the blend banburying, carried out hot pressing in 1-5 minute successively and colded pressing in 10-30 minute after 160-170 ℃ of following preheating 2-5 minute, pressure is 13-18MPa.
5. according to the plasticization and modification method of the described poly(lactic acid) of above-mentioned arbitrary claim, it is characterized in that, described poly(lactic acid), tributyl citrate and hexanaphthene-1, the part by weight of 2-dicarboxyl dinonyl is 100: 5-20: 5-20.
6. according to the plasticization and modification method of arbitrary described poly(lactic acid) in the claim 1 to 4, it is characterized in that, the melting index of described poly(lactic acid) is (190 ℃, 2.16kg) 5-12g/10min, promptly at 190 ℃, 2.16kg load under, the melt of poly(lactic acid) is by a diameter 2.1mm pipe, effusive quality is 5-12g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010618280 CN102040815A (en) | 2010-12-30 | 2010-12-30 | Method for plasticizing and modifying polylactic acid |
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| CN 201010618280 CN102040815A (en) | 2010-12-30 | 2010-12-30 | Method for plasticizing and modifying polylactic acid |
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| CN 201010618280 Pending CN102040815A (en) | 2010-12-30 | 2010-12-30 | Method for plasticizing and modifying polylactic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107075218A (en) * | 2014-10-22 | 2017-08-18 | 韩华化学株式会社 | The plasticizer composition of compound comprising (2 ethylhexyl) ester of 1,4 dicarboxylic acids of hexamethylene two and based on citrate and the vinyl chloride resin composition for including the plasticizer composition |
| CN112041383A (en) * | 2018-06-12 | 2020-12-04 | 株式会社Lg化学 | Plasticizer composition and resin composition comprising the same |
-
2010
- 2010-12-30 CN CN 201010618280 patent/CN102040815A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 20101015 王如寅 聚乳酸增韧改性及其机理研究 B016-20 1-6 , 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107075218A (en) * | 2014-10-22 | 2017-08-18 | 韩华化学株式会社 | The plasticizer composition of compound comprising (2 ethylhexyl) ester of 1,4 dicarboxylic acids of hexamethylene two and based on citrate and the vinyl chloride resin composition for including the plasticizer composition |
| CN112041383A (en) * | 2018-06-12 | 2020-12-04 | 株式会社Lg化学 | Plasticizer composition and resin composition comprising the same |
| US11629116B2 (en) | 2018-06-12 | 2023-04-18 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
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Application publication date: 20110504 |