CN103819690B - Degraded null method prepares the technique of high-crystallinity poly(lactic acid) - Google Patents
Degraded null method prepares the technique of high-crystallinity poly(lactic acid) Download PDFInfo
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- CN103819690B CN103819690B CN201410054739.0A CN201410054739A CN103819690B CN 103819690 B CN103819690 B CN 103819690B CN 201410054739 A CN201410054739 A CN 201410054739A CN 103819690 B CN103819690 B CN 103819690B
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Abstract
The present invention relates to the technique that a kind of null method of degrading prepares high-crystallinity poly(lactic acid), the degradable character of this technology utilization poly(lactic acid), and crystalline state and the larger feature of amorphous poly lactic acid degradation speed difference, by the amorphous areas in degraded removing material, retain crystalline domain, to improve the overall degree of crystallinity of poly-lactic acid material.Compared with prior art, the inventive method is simple, and the effect promoting degree of crystallinity can be controlled by degradation time.
Description
Technical field
The invention belongs to the technical field such as material and chemical industry, be specifically related to a kind of technology using degraded null method to prepare high-crystallinity poly(lactic acid).
Background technology
Poly(lactic acid) (PolylacticAcid or Polylactide, abbreviation: PLA), be a kind of thermoplastic aliphatic's polyester.The raw material of production poly(lactic acid) can by obtaining (i.e. so-called Corn Plastic) after reproducible Biological resources fermentation, dehydration, purifying, and poly-lactic acid products can by various mode fast degradation, final degraded product is water and carbonic acid gas, non-environmental-pollution.Therefore poly(lactic acid) is considered to a kind of environmental protection plastics possessing good use properties.
The fusing point of poly(lactic acid), thermotolerance, mechanical property, processing characteristics are all relevant with its degree of crystallinity, therefore how to regulate and change the emphasis that degree of crystallinity is poly-lactic acid material.The poly(lactic acid) thermal characteristics of high-crystallinity and better mechanical property, the chances are 37% for the degree of crystallinity of such as poly (l-lactic acid), and its second-order transition temperature is approximately 65 DEG C, and fusing point is 180 DEG C, and tensile modulus is approximately 3-4GPa, and modulus in flexure is approximately 4-5GPa.And poly (l-lactic acid) blended with poly-D-ALPHA-Hydroxypropionic acid according to a certain percentage after, degree of crystallinity can bring up to about 50%, and fusing point can improve at most 50 DEG C, and Heat Deflection Temperature improves about 60 DEG C and has been elevated to 190 DEG C.The heat impedance poly(lactic acid) of gained can use under the environment of 110 DEG C.Poly(lactic acid) is similar with the mechanical properties of polystyrene, PETE, but the temperature that can use continuously is much lower, and degree of crystallinity can improve the temperature that can use continuously after improving.
Current raising polylactic acid crystal degree has multiple method, common are doping vario-property method, such as, in poly(lactic acid), adds nucleator, to improve crystal property, or by poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid racemize blended, also can improve degree of crystallinity.But various method has respective shortcoming, how to study the method that makes new advances to improve polylactic acid crystal degree and corresponding engineering property, be still the focus studied at present in the field in.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of simple, fast and reliable degraded null method to prepare the technique of high-crystallinity poly(lactic acid).
Object of the present invention can be achieved through the following technical solutions: a kind of null method of degrading prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, the degradable character of this technology utilization poly(lactic acid), and crystalline state and the larger feature of amorphous poly lactic acid degradation speed difference, by the amorphous areas in degraded removing material, retain crystalline domain, to improve the overall degree of crystallinity of poly-lactic acid material.
Described technique specifically comprises the following steps:
(1) in poly(lactic acid), nucleator melt blending is added, and/or annealing process, obtain the product of high-crystallinity;
(2) step (1) products therefrom is placed in degradation solution, it is weightless that timing weighs monitoring, when obvious slope variation appears in degradation speed and the linear fit curve of time, takes out material, namely obtain the poly-lactic acid products of high-crystallinity.
Poly(lactic acid) described in step (1) is pretreated poly(lactic acid), and described pre-treatment, for poly(lactic acid) is heated to 150 ~ 180 DEG C of meltings, pours into board mould, make the shape that specific surface area is easy to more greatly overall degraded, comprise particle, sheet material, wire rod or Multi-hole section.
Described nucleator comprises talcum powder, silicon-dioxide, polynite, metal phosphate, aluminium salt, one or more in high-grade aliphatic ester, fatty amide; The add-on of nucleator is the 0.1-7% of poly(lactic acid) weight.
Described annealing process cools with the speed of 10 ~ 60 DEG C/h.
Described degradation solution comprises the hydrochloric acid of concentration 0.01mol/L-0.5mol/L, sulfuric acid or salpeter solution, the sodium hydroxide of 0.01mol/L-0.5mol/L or potassium hydroxide solution, water, or concentration is 0.01mol/L-0.5mol/L salts solution.
The poly-lactic acid products of step (2) gained high-crystallinity is broken shape, again can be processed by the poly-lactic acid products of described high-crystallinity as required and be integrated into required form, and described processing is integrated and comprised pelletizing bonding, or colds pressing.
Compared with prior art, the present invention is the degradation property utilizing poly(lactic acid) autologous, removes amorphous region to improve degree of crystallinity, does not therefore need to rely on modified method, can retain performance or the formation of required poly-lactic acid material, and reach higher degree of crystallinity.Simultaneously due to the good degradation property of poly(lactic acid), present method is simple, and the effect promoting degree of crystallinity can be controlled by degradation time.
Accompanying drawing explanation
Fig. 1 is the linear fit graphic representation of degradation rate V and time t in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
1) trade mark 2003D poly(lactic acid) is heated to 160 degrees Celsius of meltings, pours into board mould, 2) start cooling from 160 degrees Celsius, per hourly fall 10 degree, be down to 100 degrees Celsius to place 12 hours, continue, with the speed of 10 degree of/hour cooling, to obtain the plate product of high-crystallinity.
2) product is placed in 0.5mol/LNaOH, it is weightless that timing weighs monitoring.When obvious slope variation appears in the linear fit curve of degradation speed V and time t, as shown in Figure 1, take out material, namely obtain the poly-lactic acid products of high-crystallinity, now material should be broken shape.
Embodiment 2
1) poly(lactic acid) of trade mark 2003D is added the granulation of polynite nucleator blending extrusion.
2) poly(lactic acid) of modification is processed into the filamentary material of diameter 2mm.In the course of processing, controlled cooling model speed is 60 Celsius degrees/hour, to obtain higher degree of crystallinity product.
3) product is placed in 0.1mol/L hydrochloric acid, it is weightless that timing weighs monitoring.When obvious slope variation appears in the linear fit curve of degradation speed vs time, take out material, namely obtain the poly-lactic acid products of high-crystallinity, now material should be broken shape.
4) by broken material pelletizing, and bind with the saturated chloroformic solution of poly(lactic acid), be pressed into desired shape.After drying solvent, be namely fixed the high-crystallinity poly(lactic acid) solid of shape.
Embodiment 3
1) poly(lactic acid) of trade mark 4032D is added the granulation of metal phosphate nucleator blending extrusion.
2) poly(lactic acid) of modification be processed into the filamentary material of diameter 2mm and shred granulation.In the course of processing, controlled cooling model speed is 30 Celsius degrees/hour, to obtain higher degree of crystallinity product.
3) product is placed in pure water, it is weightless that timing weighs monitoring.When obvious slope variation appears in the linear fit curve of degradation speed vs time, take out material, namely obtain the poly-lactic acid products of high-crystallinity, now material should be broken shape.
4) broken material granule is put into mould, add tetrahydrofuran solvent by the quality proportioning of 5%, solvent penetration is evenly colded pressing with the pressure of 0.5Mpa afterwards, after drying solvent, is namely fixed the high-crystallinity poly(lactic acid) solid of shape.
Embodiment 4
A kind of null method of degrading prepares the technique of high-crystallinity poly(lactic acid), the degradable character of technology utilization poly(lactic acid), and crystalline state and the larger feature of amorphous poly lactic acid degradation speed difference, by the amorphous areas in degraded removing material, retain crystalline domain, to improve the overall degree of crystallinity of poly-lactic acid material.Specifically comprise the following steps:
(1) for poly(lactic acid) is heated to 150 DEG C of meltings, pour into board mould, make the particle shape that specific surface area is easy to more greatly overall degraded, in poly(lactic acid), then add nucleator silicon-dioxide melt blending, be cooled to room temperature with the speed of 10 DEG C/h again, obtain the product of high-crystallinity; The add-on of nucleator is the 0.1-7% of poly(lactic acid) weight.
(2) step (1) products therefrom is placed in degradation solution 0.0lmol/L sulfuric acid, it is weightless that timing weighs monitoring, when obvious slope variation appears in degradation speed and the linear fit curve of time, take out material, namely obtain the poly-lactic acid products of high-crystallinity.
The poly-lactic acid products of step (2) gained high-crystallinity is broken shape, again can be processed by the poly-lactic acid products of described high-crystallinity as required and be integrated into required form, and described processing is integrated and comprised pelletizing bonding, or colds pressing.
Embodiment 5
A kind of null method of degrading prepares the technique of high-crystallinity poly(lactic acid), the degradable character of technology utilization poly(lactic acid), and crystalline state and the larger feature of amorphous poly lactic acid degradation speed difference, by the amorphous areas in degraded removing material, retain crystalline domain, to improve the overall degree of crystallinity of poly-lactic acid material.Specifically comprise the following steps:
(1) for poly(lactic acid) is heated to 180 DEG C of meltings, pour into board mould, make the sheet material that specific surface area is easy to more greatly overall degraded, in poly(lactic acid), then add nucleator fatty amide melt blending, be cooled to room temperature with the speed of 60 DEG C/h again, obtain the product of high-crystallinity; The add-on of nucleator is the 0.1-7% of poly(lactic acid) weight.
(2) step (1) products therefrom is placed in degradation solution 0.5mol/LKCl, it is weightless that timing weighs monitoring, when obvious slope variation appears in degradation speed and the linear fit curve of time, take out material, namely obtain the poly-lactic acid products of high-crystallinity.
The poly-lactic acid products of step (2) gained high-crystallinity is broken shape, again can be processed by the poly-lactic acid products of described high-crystallinity as required and be integrated into required form, and described processing is integrated and comprised pelletizing bonding, or colds pressing.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to structure of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.
Claims (6)
1. a null method of degrading prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, the degradable character of this technology utilization poly(lactic acid), and crystalline state and the larger feature of amorphous poly lactic acid degradation speed difference, by the amorphous areas in degraded removing material, retain crystalline domain, to improve the overall degree of crystallinity of poly-lactic acid material;
Described technique specifically comprises the following steps:
(1) in poly(lactic acid), nucleator melt blending is added, and/or annealing process, obtain the product of high-crystallinity;
(2) step (1) products therefrom is placed in degradation solution, it is weightless that timing weighs monitoring, when obvious slope variation appears in degradation speed and the linear fit curve of time, takes out material, namely obtain the poly-lactic acid products of high-crystallinity.
2. a kind of null method of degrading according to claim 1 prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, poly(lactic acid) described in step (1) is pretreated poly(lactic acid), described pre-treatment is for be heated to 150 ~ 180 DEG C of meltings by poly(lactic acid), pour into board mould, make the shape that specific surface area is easy to more greatly overall degraded, comprise particle, sheet material, wire rod or Multi-hole section.
3. a kind of null method of degrading according to claim 1 prepares the technique of high-crystallinity poly(lactic acid), and it is characterized in that, described nucleator comprises talcum powder, silicon-dioxide, polynite, metal phosphate, aluminium salt, one or more in high-grade aliphatic ester, fatty amide; The add-on of nucleator is the 0.1-7% of poly(lactic acid) weight.
4. a kind of null method of degrading according to claim 1 prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, described annealing process cools with the speed of 10 ~ 60 DEG C/h.
5. a kind of null method of degrading according to claim 1 prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, described degradation solution comprises the hydrochloric acid of concentration 0.01mol/L-0.5mol/L, sulfuric acid or salpeter solution, the sodium hydroxide of 0.01mol/L-0.5mol/L or potassium hydroxide solution, water, or concentration is 0.01mol/L-0.5mol/L salts solution.
6. a kind of null method of degrading according to claim 1 prepares the technique of high-crystallinity poly(lactic acid), it is characterized in that, the poly-lactic acid products of step (2) gained high-crystallinity is broken shape, as required the poly-lactic acid products of described high-crystallinity can be processed again and be integrated into required form, described processing is integrated and is comprised pelletizing bonding, or colds pressing.
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| CN107236147B (en) * | 2017-05-09 | 2019-07-19 | 北京航空航天大学 | A kind of method of crystalline plastics high-performance bio degradation |
| CN109294181A (en) * | 2017-07-24 | 2019-02-01 | 寀呈股份有限公司 | The manufacturing method of polylactic acid constituent and polylactic acid molded product |
| CN108310458B (en) * | 2018-03-21 | 2021-05-11 | 奚桢浩 | Method for preparing tissue engineering scaffold material by adopting degradable synthetic polymer material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452618A (en) * | 2000-03-23 | 2003-10-29 | 布鲁塞尔生物技术 | Method for purifying cyclic esters |
| CN1534052A (en) * | 2003-03-31 | 2004-10-06 | 世韩工业株式会社 | Saturated polyester possessing excellent crystallization property |
| CN102941640A (en) * | 2012-10-09 | 2013-02-27 | 四川大学 | High pressure forming method for increasing crystallinity of polylactic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452618A (en) * | 2000-03-23 | 2003-10-29 | 布鲁塞尔生物技术 | Method for purifying cyclic esters |
| CN1534052A (en) * | 2003-03-31 | 2004-10-06 | 世韩工业株式会社 | Saturated polyester possessing excellent crystallization property |
| CN102941640A (en) * | 2012-10-09 | 2013-02-27 | 四川大学 | High pressure forming method for increasing crystallinity of polylactic acid |
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