CN101168616A - Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material - Google Patents
Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material Download PDFInfo
- Publication number
- CN101168616A CN101168616A CNA2007100534210A CN200710053421A CN101168616A CN 101168616 A CN101168616 A CN 101168616A CN A2007100534210 A CNA2007100534210 A CN A2007100534210A CN 200710053421 A CN200710053421 A CN 200710053421A CN 101168616 A CN101168616 A CN 101168616A
- Authority
- CN
- China
- Prior art keywords
- nanometer
- mixture
- polymer particle
- poly
- lactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a preparation method of polysaccharide nanometer granule grafting polyester modification lactic acid material. The invention is characterized in that the preparation method comprises the following steps: firstly, according to the 1:1-500 mass ratio of polysaccharide nanometer granule and polymerization monomer, the polysaccharide nanometer granule and the polymerization monomer are chosen and then are mixed, catalyst is added into, the mass of the catalyst is 0.01-5 percent of mass of the polymerization monomer, and then the polysaccharide nanometer granule, the polymerization monomer and the catalyst are mixed evenly, and then mixture A is obtained; and then thermal polymerization or microwave assisted polymerization is adopted; secondly, methylene chloride is added into mixture B to be disloved, methyl alcohol is added to deposit, deposited matter is filtered, washed and dried, and then polysaccharide nanometer granule grafting polyester is obtained; thirdly, according to the mass percent of 0.01-95 percent of polysaccharide nanometer granule grafting polyester and 5-99.99 percent of polylactic acid, the melt blending, the solution blending or the extrusion blending is adopted, and a polysaccharide nanometer granule grafting polyester modification lactic acid material product can be obtained. The invention has the advantages that the cost is low, the environment is protected, the degradation is easy, and the process is simple.
Description
Technical field
The present invention relates to a kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, belong to degradable ecological environment material nd field, also belong to field of biomedical materials.
Background technology
Natural macromolecular material has renewable, and therefore advantages of environment protection develops the focus that the natural macromolecular material product becomes various countries' research in recent years.The intravital poly-polysaccharide xln of animal and plant disperses back formation stabilized nano structure in solution through acid or alkaline purification and method such as ultrasonic, mainly is rod-like crystal whisker (as Mierocrystalline cellulose and chitin whisker) and lamella nanocrystalline (as nanometer starch crystal).Inorganic nano-particle is (as layered silicate, carbon nanotube, nanometer SiO
2) to the obvious raising of polymer materials mechanical property and thermal characteristics, impel the research of nano composite material to deepen continuously and obtained many industrialization achievements.Simultaneously, the safety and health problem of nano-scale also is suggested, and comes into one's own day by day.Natural polysaccharide has biological degradability and biocompatibility, and the accumulation that causes after can avoiding inorganic nano-particle to use also helps reclaiming polymeric matrix, can also avoid inorganic nano-particle to influence that safety and health caused.Simultaneously, natural polysaccharide whisker and platelet can have been given play to the function as the inorganic nano-particle strongthener based on high-specific surface area and the rigid rod and the sheet structure of nanoscale.At present, utilize natural polysaccharide nano whisker and platelet successfully enhancing modified rubber (Biomacromolecules 2006,6,612; Biomacromolecules 2003,4, and 1835; Macromolecules 2005,38,3783), (Biomacromolecules 2006 for starch plastic, 7,531), (Biomacromolecules 2005 for the poly(lactic acid) plastics, 6,3160), (Macromolecules 2002 for polycaprolactone, 35,2190), (Polymer 2005 for polyvinyl alcohol, 46,5637), polypropylene, polyvinyl chloride, plastic of soybean protein etc., what be worth especially proposing is that the starch nano platelet that extracts from starch is also demonstrating tangible reinforced effects with the starch plastic compound tense.Aspect practical application, Italy Novamont company and Goodyear tire and rubber company have utilized the nanoparticle that extracts from starch partly to replace traditional rubber reinforcing filler-carbon black and silicon-dioxide, develop tire (the Europe Patent of eco-friendly low-rolling-resistance, EP995775A1,2000).In addition, the Mierocrystalline cellulose whisker also is used to strengthen the polyelectrolyte that contains lithium ion, can be used as lithium cell starting material (ElectrochimActa 2005,50,3897; Macromolecules 2004,37, and 4839; J Appl Polym Sci 2004,93,2883).
The exploitation of high-performance poly lactate material is achieved via dual mode usually: the one, and the molecular weight of raising poly(lactic acid); The 2nd, carry out modification by the compound new technology of material.At present, there is very big difficulty in the production of poly-lactic acid in high molecular weight product on technology and technology, and the cost height, has restricted the application of poly(lactic acid) in the wrapping material field.Compound by introducing other component and poly(lactic acid), not only can give the poly(lactic acid) high-performance, can also create very big cost and reduce the space, technology is also simple simultaneously.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, environmental protection, the easy preparation method of degraded, the simple polysaccharide nano particle grafting polyester modified polylactic acid material of technology.
To achieve these goals, the technical solution adopted in the present invention is: a kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material is characterized in that it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 1-500, choose nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is the 0.01-5% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt thermopolymerization or microwave-assisted polymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into oil bath in 70-120 ℃ of following polyreaction 1-48 hour, has reacted the back and has taken out, cools off, and obtains mixture B;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 50-800 watt, and the time is 1-20 minute, has reacted the back and has taken out, cools off, and obtains mixture B;
Described nanometer polyose polymer particle is any one or any one the above mixture in Mierocrystalline cellulose whisker, chitin whisker, the nanometer starch crystal, and during any one above mixing, each component is any proportioning; Described polymerization single polymerization monomer is caprolactone or rac-Lactide; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 0.01-95, poly(lactic acid) 5-99.99 chooses nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending, solution blending then or extrudes blend;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 80-190 ℃, the Banbury mixer rotating speed is 10-150rpm, time is 1-30 minute, mix back gained material and carry out hot-forming or injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 1-50%, the mass concentration of poly(lactic acid) solution is 1-50%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding;
Extruding blend is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize forcing machine that both are extruded blend, the temperature of extruding each section of blend interval is 80-190 ℃, and screw speed is 50-150rpm; The gained extrudate carries out hot-forming or injection moulding, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Nanometer polyose polymer particle forms homogeneous and continuous phase structure by graft polymerization grafting polymer segment, can improve the performance of material well.As passing through g-polycaprolactone (or poly(lactic acid)) on Mierocrystalline cellulose whisker, nanometer starch crystal, be used to strengthen poly-lactic acid material, according to the common external phase structure of its nano effect and formation, improved the intensity and the elongation of material significantly, reach the toughness reinforcing effect of synchronous enhancing.
The present invention at first carries out the graft polymerization monomer to nanometer polyose polymer particle, gets nanometer polyose polymer particle grafted polyester, passes through the physical blending method with poly(lactic acid) again, obtains the polysaccharide nano particle grafting polyester modified polylactic acid material of complete biodegradable; Can produce high-fall packaging film of separating of high-performance and container according to type used and service requirements.The enhancement of polysaccharide nano particle grafting polyester modified polylactic acid material mainly gives the credit to high surface, high-specific surface area, the rigidity of nanometer polyose polymer particle, and can form common external phase structure and strong interface interaction by polycaprolactone (or poly(lactic acid)) chain and poly(lactic acid) matrix behind grafting and modifying.Compare with inorganic nano-particle, nanometer polyose polymer particle grafted polycaprolactone (or poly(lactic acid)) has biological degradation and biocompatibility, and therefore the polysaccharide nano particle grafting polyester modified polylactic acid material fully biodegradable of exploitation can't be detrimental to health.
The present invention can make full use of advantages such as the environmental friendliness of natural macromolecular material (nanometer polyose polymer particle), easy degraded, meets the requirement of Sustainable development; The polysaccharide nano particle grafting polyester modified polylactic acid material that obtains is both environmentally friendly harmless, can satisfy the use properties requirement of material again, has improved the performance of synthetic materials; Advantage such as that the present invention has is with low cost, nontoxic, environmental protection, fully biodegradable, technology are simple.Product of the present invention can be used for multiple uses such as packing, biology, medical science.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of Mierocrystalline cellulose whisker and caprolactone is 1: 40, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 80 watts, and the time is 5 minutes; With it taking-up,, polyreaction is stopped after having reacted, obtain mixture B with being water-cooled to below 50 ℃;
2) add methylene dichloride (Shanghai chemical reagents corporation of Chinese Medicine group) dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 200% of mixture B quality that methylene dichloride adds quality; Add methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) precipitation in the mixture C, it is 500% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester is respectively: 1,2,4,8,12, poly(lactic acid) corresponded to for 99,98,96,92,88 (pure poly(lactic acid) is used to do contrast) respectively, choose 5 groups of nanometer polyose polymer particle grafted polyesters, poly(lactic acid), adopt solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 20%, the mass concentration of poly(lactic acid) solution is 20%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of the film material of polysaccharide nano particle grafting polyester modified polylactic acid material preparation sees Table 1.Mechanical property thinks carefully newly in Shenzhen with reference to IS06239-1986 (E) standard on the CMT6503 instrument of testing tool company and records that rate of extension is 10mm/min, and is as follows.
Embodiment 2:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of Mierocrystalline cellulose whisker and caprolactone is 1: 40, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 160 watts, and the time is 3 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add methylene dichloride (Shanghai chemical reagents corporation of Chinese Medicine group) dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 200% of mixture B quality that methylene dichloride adds quality; Add methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) precipitation in the mixture C, it is 300% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester is respectively: 1,2,4,8, and poly(lactic acid) then corresponds to 99,98,96,92 respectively, chooses 4 groups of nanometer polyose polymer particle grafted polyesters, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 30%, the mass concentration of poly(lactic acid) solution is 30%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of the film material of polysaccharide nano particle grafting polyester modified polylactic acid material preparation sees Table 1.
Embodiment 3:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of Mierocrystalline cellulose whisker and caprolactone is 1: 40, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 160 watts, and the time is 5 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 300% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 500% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester is respectively: 1,2,4,8, and poly(lactic acid) then corresponds to 99,98,96,92 respectively, chooses nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 40%, the mass concentration of poly(lactic acid) solution is 40%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of the film material of polysaccharide nano particle grafting polyester modified polylactic acid material preparation sees Table 1.
Embodiment 4:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of chitin whisker and caprolactone is 1: 50, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.5% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 200 watts, and the time is 8 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 600% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 600% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 50, poly(lactic acid) 50 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 80 ℃, the Banbury mixer rotating speed is 50rpm, time is 15 minutes, mix back gained material and carry out injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product;
Embodiment 5:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) nanometer starch crystal that pea starch (Canadian Pea company limited) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of nanometer starch crystal and caprolactone is 1: 40, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 160 watts, and the time is 7 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 300% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 300% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester is respectively: 10,20,30,40,50, and poly(lactic acid) then corresponds to 90,80,70,60,50 respectively, chooses nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 10%, the mass concentration of poly(lactic acid) solution is 10%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of the film material of polysaccharide nano particle grafting polyester modified polylactic acid material preparation sees Table 2.
Embodiment 6:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) nanometer starch crystal that pea starch (Canadian Pea company limited) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of nanometer starch crystal and caprolactone is 1: 10, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 240 watts, and the time is 5 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 1000% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 1000% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester is respectively: 5,10,15,20,25,30, poly(lactic acid) then corresponds to 95,90,85,80,75,70 respectively, choose 6 groups of nanometer polyose polymer particle grafted polyesters, poly(lactic acid), adopt solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 20%, the mass concentration of poly(lactic acid) solution is 20%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of the film material of polysaccharide nano particle grafting polyester modified polylactic acid material preparation sees Table 2.
Embodiment 7:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted mixes in container with rac-Lactide (U.S. Aldrich company); the mass ratio of Mierocrystalline cellulose and rac-Lactide is 1: 1; add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer; it is 1% of rac-Lactide quality that stannous octoate adds quality; mix, obtain mixture
A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 100 watts, and the time is 10 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 400% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 400% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 50, poly(lactic acid) 50 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 30%, the mass concentration of poly(lactic acid) solution is 30%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 8:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of Mierocrystalline cellulose whisker and caprolactone is 1: 9, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 1.9% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, put into oil bath in 110 ℃ of following polyreactions 1 hour, reacted the back and taken out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 100% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 200% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 30, poly(lactic acid) 70 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 105 ℃, the Banbury mixer rotating speed is 30rpm, time is 23 minutes, mixing back gained material carries out hot-forming, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 9:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of chitin whisker and caprolactone is 1: 5, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.5% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, put into oil bath in 100 ℃ of following polyreactions 20 hours, reacted the back and taken out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 500% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 500% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 10, poly(lactic acid) 90 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 120 ℃, the Banbury mixer rotating speed is 50rpm, time is 12 minutes, mix back gained material and carry out injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 10:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of chitin whisker and caprolactone is 1: 30, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 0.4% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 100 watts, and the time is 10 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 1000% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 1000% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 40, poly(lactic acid) 60 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 20%, the mass concentration of poly(lactic acid) solution is 20%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 11:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) nanometer starch crystal that pea starch (Canadian Pea company limited) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of nanometer starch crystal and caprolactone is 1: 70, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, put into oil bath in 115 ℃ of following polyreactions 6 hours, reacted the back and taken out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 200% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 200% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 70, poly(lactic acid) 30 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 30%, the mass concentration of poly(lactic acid) solution is 30%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 12:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) nanometer starch crystal that W-Gum (French Roquette Freres S.A. company) is extracted mixes in container with caprolactone (U.S. Aldrich company), the mass ratio of nanometer starch crystal and caprolactone is 1: 70, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 1% of caprolactone quality that stannous octoate adds quality, mix, obtain mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, put into oil bath in 115 ℃ of following polyreactions 6 hours, reacted the back and taken out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 400% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 400% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 70, poly(lactic acid) 30 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 115 ℃, the Banbury mixer rotating speed is 60rpm, time is 20 minutes, mixing back gained material carries out hot-forming, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 13:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that linters (Xiangfan sky above Hubei and Hunan chemical fibre limited liability company) is extracted, the nanometer starch crystal that W-Gum (French RoquetteFreres S.A. company) extracts, the chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) extracts, (U.S. Aldrich company) mixed in container with rac-Lactide, the Mierocrystalline cellulose whisker, the composition of nanometer starch crystal and chitin whisker and the mass ratio of rac-Lactide are 1: 50, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 1% of rac-Lactide quality that stannous octoate adds quality, each constituent mass per-cent is in the composition: Mierocrystalline cellulose whisker 40, nanometer starch crystal 20, chitin whisker 40; Mix, obtain mixture A; Adopt the microwave-assisted polymerization then:
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 300 watts, and the time is 10 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 500% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 500% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 60, poly(lactic acid) 40 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 100 ℃, the Banbury mixer rotating speed is 70rpm, time is 20 minutes, mix back gained material and carry out injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 14:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that Mierocrystalline cellulose (Shanghai chemical reagents corporation of Chinese Medicine group) is extracted, the nanometer starch crystal that yam starch (Shanghai chemical reagents corporation of Chinese Medicine group) extracts, the chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) extracts, (U.S. Aldrich company) mixed in container with caprolactone, the Mierocrystalline cellulose whisker, the composition of nanometer starch crystal and chitin whisker and the mass ratio of caprolactone are 1: 75, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 2% of caprolactone quality that stannous octoate adds quality, each constituent mass per-cent is in the composition: Mierocrystalline cellulose whisker 50, nanometer starch crystal 20, chitin whisker 30; Mix, obtain mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes 30 minutes, and mixture A is remained in the encloses container of vacuum, put into oil bath in 120 ℃ of following polyreactions 25 hours, reacted the back and taken out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 300% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 300% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 70, poly(lactic acid) 30 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 15%, the mass concentration of poly(lactic acid) solution is 15%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding; Promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 15:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) the Mierocrystalline cellulose whisker that Mierocrystalline cellulose (Shanghai chemical reagents corporation of Chinese Medicine group) is extracted, the nanometer starch crystal that yam starch (Shanghai chemical reagents corporation of Chinese Medicine group) extracts, the chitin whisker that chitin (Zhejiang Province gold shell Biochemie Co., Ltd) extracts, (U.S. Aldrich company) mixed in container with caprolactone, the Mierocrystalline cellulose whisker, the composition of nanometer starch crystal and chitin whisker and the mass ratio of caprolactone are 1: 50, add stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and make catalyzer, it is 1.5% of caprolactone quality that stannous octoate adds quality, each constituent mass per-cent is in the composition: Mierocrystalline cellulose whisker 20, nanometer starch crystal 40, chitin whisker 40; Mix, obtain mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumized 30 minutes, mixture A is remained in the encloses container of vacuum, put into microwave and react, reaction power is 200 watts, and the time is 10 minutes, having reacted the back takes out, with being water-cooled to below 50 ℃, polyreaction is stopped, obtaining mixture B;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C, it is 200% of mixture B quality that methylene dichloride adds quality; Add methanol extraction in the mixture C, it is 200% of methylene dichloride quality that methyl alcohol adds quality, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 70, poly(lactic acid) 30 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts then and extrudes blend;
Extruding blend is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize forcing machine that both are extruded blend, forcing machine is equipped with seven temperature provinces, be respectively 90,100,120,140,155,160 and 155 ℃ from sampler to the extrusion temperature setting, end temp is 155 ℃, and screw speed is 60rpm.The gained extrudate carries out hot-forming, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 16:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 1, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 0.01% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into oil bath in 70 ℃ of following polyreactions 1 hour, has reacted that take out the back, cooling, obtains mixture B;
Described nanometer polyose polymer particle is the Mierocrystalline cellulose whisker; Described polymerization single polymerization monomer is a caprolactone; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 0.01, poly(lactic acid) 99.99 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 80 ℃, the Banbury mixer rotating speed is 10rpm, time is 1 minute, mixing back gained material carries out hot-forming, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 17:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 500, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 5% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into oil bath in 120 ℃ of following polyreactions 48 hours, has reacted that take out the back, cooling, obtains mixture B;
Described nanometer polyose polymer particle is the Mierocrystalline cellulose whisker; Described polymerization single polymerization monomer is a caprolactone; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 95, poly(lactic acid) 5 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending then;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 190 ℃, the Banbury mixer rotating speed is 150rpm, time is 30 minutes, mix back gained material and carry out hot-forming or injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 18:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 1, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 0.01% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 50 watts, and the time is 20 minutes, has reacted the back and has taken out, cools off, and obtains mixture B;
Described nanometer polyose polymer particle is a chitin whisker; Described polymerization single polymerization monomer is a rac-Lactide; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 0.01, poly(lactic acid) 99.99 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 1%, the mass concentration of poly(lactic acid) solution is 1%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding.
Embodiment 19:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 500, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 5% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 800 watts, and the time is 1 minute, has reacted the back and has taken out, cools off, and obtains mixture B;
Described nanometer polyose polymer particle is a chitin whisker; Described polymerization single polymerization monomer is a rac-Lactide; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 95, poly(lactic acid) 5 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts solution blending then;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 50%, the mass concentration of poly(lactic acid) solution is 50%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding.
Embodiment 20:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 1, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 0.01% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt thermopolymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into oil bath in 70 ℃ of following polyreactions 48 hours, has reacted that take out the back, cooling, obtains mixture B;
Described nanometer polyose polymer particle is a nanometer starch crystal; Described polymerization single polymerization monomer is a caprolactone; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 0.01, poly(lactic acid) 99.99 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts then and extrudes blend;
Extruding blend is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize forcing machine that both are extruded blend, the temperature of extruding each section of blend interval is 80,100,140,170,190,170,155 ℃, end temp is 155 ℃, and screw speed is 50rpm; The gained extrudate carries out hot-forming, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Embodiment 21:
A kind of preparation method of polysaccharide nano particle grafting polyester modified polylactic acid material, it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 500, chooses nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is 5% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt the microwave-assisted polymerization then;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 800 watts, and the time is 1 minute, has reacted the back and has taken out, cools off, and obtains mixture B;
Described nanometer polyose polymer particle is a nanometer starch crystal; Described polymerization single polymerization monomer is a rac-Lactide; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 95, poly(lactic acid) 5 is chosen nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts then and extrudes blend;
Extruding blend is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize forcing machine that both are extruded blend, the temperature of extruding each section of blend interval is that the temperature of extruding each section of blend interval is 100,140,170,190,170,160,155 ℃, end temp is 155 ℃, and screw speed is 150rpm; The gained extrudate carries out injection moulding, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
The mechanical property of table 1 polysaccharide nano particle grafting polyester modified polylactic acid material (Mierocrystalline cellulose whisker g-polycaprolactone polydactyl acid) casting film-forming
| Embodiment | Reaction conditions | The content of nanometer polyose polymer particle grafted polyester | Test σ b/ MPa | True σ b/MPa | ε b/％ | E/MPa |
| Embodiment 1 | 1∶40 80W/5min | 0 | 34.26 | 40.7 | 18.81 | 1565.95 |
| 1 | 78.77 | 83.47 | 5.96 | 5562.23 | ||
| 2 | 30.87 | 42.87 | 38.89 | 1718.95 | ||
| 4 | 20.35 | 31.49 | 54.76 | 1362.45 | ||
| 8 | 15.04 | 24.1 | 60.27 | 1355.98 | ||
| 12 | 9.76 | 22.34 | 128.91 | 705.58 | ||
| Embodiment 2 | 1∶40 160W/3min | 1 | 30.38 | 35.1 | 15.53 | 1533.62 |
| 2 | 23.50 | 30.14 | 28.23 | 1505.99 | ||
| 4 | 21.42 | 28.73 | 34.13 | 1254.35 |
| 8 | 29.81 | 55.65 | 86.69 | 1477.67 | ||
| Embodiment 3 | 1∶40 160W/5min | 1 | 18.45 | 23.52 | 27.51 | 1140.89 |
| 2 | 17.01 | 27.23 | 59.56 | 1057.83 | ||
| 4 | 22.26 | 35.52 | 59.6 | 985.43 | ||
| 8 | 34.81 | 75.48 | 116.82 | 813.38 |
The mechanical property of table 2 polysaccharide nano particle grafting polyester modified polylactic acid material (nanometer starch crystal g-polycaprolactone polydactyl acid) casting film-forming
| Embodiment | Reaction conditions | The content of nanometer polyose polymer particle grafted polyester | Test σ b/MPa | True σ b/MPa | ε b/％ | E/MPa |
| Embodiment 5 | 1∶40 160W/7min | 0 | 34.26 | 40.7 | 18.81 | 1565.95 |
| 10 | 20.19 | 75.38 | 273.38 | 1104.53 | ||
| 20 | 17.38 | 54.18 | 211.70 | 1056.84 | ||
| 30 | 14.19 | 21.47 | 51.32 | 1016.37 | ||
| 40 | 24.12 | 26.63 | 10.41 | 1070.09 | ||
| 50 | 14.55 | 14.82 | 1.89 | 908.19 | ||
| Embodiment 6 | 1∶10 240W/5min | 5 | 26.43 | 57.18 | 134.65 | 1488.64 |
| 10 | 20.17 | 40.13 | 125.33 | 1579.78 | ||
| 15 | 17.94 | 35.24 | 118.23 | 1463.16 | ||
| 20 | 15.09 | 32.94 | 113.41 | 1126.38 | ||
| 25 | 16.34 | 16.77 | 89.3 | 1311.36 | ||
| 30 | 12.07 | 12.92 | 33.55 | 863.76 |
As can be seen, test intensity improves little from table 1, table 2, but because the elongation raising, so actual strength improves clearly.Therefore can draw, nanometer polyose polymer particle grafted polyester has good modifying function to poly(lactic acid), can well improve the intensity and the elongation at break of material, makes it to have better actual application prospect.
Claims (1)
1. the preparation method of a polysaccharide nano particle grafting polyester modified polylactic acid material is characterized in that it comprises the steps:
1) mass ratio by nanometer polyose polymer particle and polymerization single polymerization monomer is 1: 1-500, choose nanometer polyose polymer particle, polymerization single polymerization monomer, and nanometer polyose polymer particle mixes with polymerization single polymerization monomer, add catalyzer again, it is the 0.01-5% of polymerization single polymerization monomer quality that catalyzer adds quality, mixes, and obtains mixture A; Adopt thermopolymerization or microwave-assisted polymerization then;
Hot polymerization is combined into: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into oil bath in 70-120 ℃ of following polyreaction 1-48 hour, has reacted the back and has taken out, cools off, and obtains mixture B;
Microwave-assisted is polymerized to: mixture A puts into container, vacuumizes, and mixture A is remained in the encloses container of vacuum, puts into microwave and reacts, and reaction power is 50-800 watt, and the time is 1-20 minute, has reacted the back and has taken out, cools off, and obtains mixture B;
Described nanometer polyose polymer particle is any one or any one the above mixture in Mierocrystalline cellulose whisker, chitin whisker, the nanometer starch crystal, and during any one above mixing, each component is any proportioning; Described polymerization single polymerization monomer is caprolactone or rac-Lactide; Described catalyzer is a stannous octoate;
2) add the methylene dichloride dissolving among the mixture B, wait mixture B dissolving fully, obtain mixture C; Add methanol extraction in the mixture C, suction filtration, washing precipitate, drying; Promptly get nanometer polyose polymer particle grafted polyester;
3) be by mass percentage: nanometer polyose polymer particle grafted polyester 0.01-95, poly(lactic acid) 5-99.99 chooses nanometer polyose polymer particle grafted polyester, poly(lactic acid), adopts melt blending, solution blending then or extrudes blend;
Melt blending is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize Banbury mixer with both melt blendings, the melt blending temperature is 80-190 ℃, the Banbury mixer rotating speed is 10-150rpm, time is 1-30 minute, mix back gained material and carry out hot-forming or injection moulding, promptly get the polysaccharide nano particle grafting polyester modified polylactic acid material product;
Solution blending is: nanometer polyose polymer particle grafted polyester, poly(lactic acid) are dissolved in respectively makes nanometer polyose polymer particle grafted polyester solution, poly(lactic acid) solution in the methylene dichloride, the mass concentration of nanometer polyose polymer particle grafted polyester solution is 1-50%, the mass concentration of poly(lactic acid) solution is 1-50%, nanometer polyose polymer particle grafted polyester solution and poly(lactic acid) solution are mixed, then flow casting molding;
Extruding blend is: nanometer polyose polymer particle grafted polyester and poly(lactic acid) are mixed and be uniformly dispersed, utilize forcing machine that both are extruded blend, the temperature of extruding each section of blend interval is 80-190 ℃, and screw speed is 50-150rpm; The gained extrudate carries out hot-forming or injection moulding, promptly gets the polysaccharide nano particle grafting polyester modified polylactic acid material product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100534210A CN101168616B (en) | 2007-09-29 | 2007-09-29 | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100534210A CN101168616B (en) | 2007-09-29 | 2007-09-29 | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101168616A true CN101168616A (en) | 2008-04-30 |
| CN101168616B CN101168616B (en) | 2010-07-21 |
Family
ID=39389398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100534210A Expired - Fee Related CN101168616B (en) | 2007-09-29 | 2007-09-29 | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101168616B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110196094A1 (en) * | 2010-02-11 | 2011-08-11 | Fpinnovations | Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) |
| CN102295827A (en) * | 2010-06-25 | 2011-12-28 | 阳新五龙兴塑业高科技材料有限公司 | Method for preparing fully biodegradable nano-composite polyester plastic |
| CN104001208A (en) * | 2014-04-22 | 2014-08-27 | 中国科学院宁波材料技术与工程研究所 | Biomacromolecule/chitin nanocrystalline composite scaffold material and preparation method thereof |
| WO2016074594A1 (en) * | 2014-11-13 | 2016-05-19 | 江南大学 | Nano cellulose modified by in situ polymerization with lactic acid and preparation method therefor |
| CN109280444A (en) * | 2018-09-25 | 2019-01-29 | 安徽省汉甲机电设备科技有限公司 | A kind of wood artwork surface aging resistant coating |
| CN110105733A (en) * | 2019-05-27 | 2019-08-09 | 江南大学 | A kind of preparation method of polylactic acid/polylactic acid grafting poly-dopamine composite material |
| CN110730792A (en) * | 2017-05-12 | 2020-01-24 | 地方独立行政法人大阪产业技术研究所 | Polylactic acid grafted cellulose nanofiber and method for producing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5540929A (en) * | 1995-03-08 | 1996-07-30 | Board Of Trustees Operating Michigan State University | Polysaccharides grafted with aliphatic polyesters derived from cyclic esters |
| CN1330686C (en) * | 2005-04-30 | 2007-08-08 | 中国科学院长春应用化学研究所 | Process for preparing surface lactic acid graft modified starch and aliphatic polyester graft copolymer |
| CN100516137C (en) * | 2007-01-18 | 2009-07-22 | 武汉理工大学 | Preparation method of full-degradation polylactic acid nano composite material |
-
2007
- 2007-09-29 CN CN2007100534210A patent/CN101168616B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8829110B2 (en) * | 2010-02-11 | 2014-09-09 | Fpinnovations | Nanocomposite biomaterials of nanocrystalline cellulose (NCC) and polylactic acid (PLA) |
| EP2534180A1 (en) * | 2010-02-11 | 2012-12-19 | FPInnovations | Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) |
| JP2013519736A (en) * | 2010-02-11 | 2013-05-30 | エフピーイノベイションズ | Nanocomposite biomaterial of nanocrystalline cellulose (NCC) and polylactic acid (PLA) |
| EP2534180A4 (en) * | 2010-02-11 | 2013-09-18 | Fpinnovations | Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) |
| US20110196094A1 (en) * | 2010-02-11 | 2011-08-11 | Fpinnovations | Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) |
| CN102295827A (en) * | 2010-06-25 | 2011-12-28 | 阳新五龙兴塑业高科技材料有限公司 | Method for preparing fully biodegradable nano-composite polyester plastic |
| CN104001208A (en) * | 2014-04-22 | 2014-08-27 | 中国科学院宁波材料技术与工程研究所 | Biomacromolecule/chitin nanocrystalline composite scaffold material and preparation method thereof |
| WO2016074594A1 (en) * | 2014-11-13 | 2016-05-19 | 江南大学 | Nano cellulose modified by in situ polymerization with lactic acid and preparation method therefor |
| CN110730792A (en) * | 2017-05-12 | 2020-01-24 | 地方独立行政法人大阪产业技术研究所 | Polylactic acid grafted cellulose nanofiber and method for producing same |
| US11046787B2 (en) * | 2017-05-12 | 2021-06-29 | Osaka Research Institute Of Industrial Science And Technology | Polylactide-grafted cellulose nanofiber and production method thereof |
| CN109280444A (en) * | 2018-09-25 | 2019-01-29 | 安徽省汉甲机电设备科技有限公司 | A kind of wood artwork surface aging resistant coating |
| CN110105733A (en) * | 2019-05-27 | 2019-08-09 | 江南大学 | A kind of preparation method of polylactic acid/polylactic acid grafting poly-dopamine composite material |
| CN110105733B (en) * | 2019-05-27 | 2020-06-19 | 江南大学 | Preparation method of polylactic acid/polylactic acid grafted polydopamine composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101168616B (en) | 2010-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Calvino et al. | Development, processing and applications of bio-sourced cellulose nanocrystal composites | |
| Sheng et al. | High-toughness PLA/Bamboo cellulose nanowhiskers bionanocomposite strengthened with silylated ultrafine bamboo-char | |
| CN101168616B (en) | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material | |
| Zhou et al. | Melt-processed poly (vinyl alcohol)/corn starch/nanocellulose composites with improved mechanical properties | |
| Zhang et al. | Improvement on the properties of microcrystalline cellulose/polylactic acid composites by using activated biochar | |
| Huang et al. | Poly (vinyl alcohol)/artificial marble wastes composites with improved melt processability and mechanical properties | |
| CN102108196B (en) | Method for preparing polylactic acid degradable material | |
| Sun et al. | Melt-processed poly (vinyl alcohol) composites filled with microcrystalline cellulose from waste cotton fabrics | |
| Kumar et al. | Physicochemical properties of the electron beam irradiated bamboo powder and its bio-composites with PLA | |
| CN101230189B (en) | Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material | |
| Yu et al. | High-performance fully bio-based poly (lactic acid)/polyamide11 (PLA/PA11) blends by reactive blending with multi-functionalized epoxy | |
| Wang et al. | Thermo-mechanical properties of the composite made of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and acetylated chitin nanocrystals | |
| CN102295827A (en) | Method for preparing fully biodegradable nano-composite polyester plastic | |
| CN103992517A (en) | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof | |
| CN101824229B (en) | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof | |
| CN105295106A (en) | Preparation method of cellulose based 3D printing wire | |
| CN104072957A (en) | Food grade biodegradable polylactic acid-based composite material and application thereof | |
| Kanabenja et al. | 3D printing filaments from plasticized Polyhydroxybutyrate/Polylactic acid blends reinforced with hydroxyapatite | |
| CN109627718B (en) | Full-biodegradable component toughened PLA composite material and preparation method thereof | |
| CN105199347A (en) | PLA (polylactic acid)/MMT (montmorillonite) degradation enhanced master batch blending modification PLA/PBAT (polyethylene terephthalate-adipic acid-butanediol copolyester) composite material and preparation method thereof | |
| Cui et al. | Fabrication of (PPC/NCC)/PVA composites with inner-outer double constrained structure and improved glass transition temperature | |
| CN105504704A (en) | Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN106674923A (en) | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film and preparation method thereof | |
| CN101851423B (en) | Thermoplastic plant protein/polyhydroxyalkanoate blend material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: WUHAN SANJIANG SPACE GOOD HANCHUAN BIO-TECH CO., L Free format text: FORMER OWNER: WUHAN UNIVERSITY OF TECHNOLOGY Effective date: 20120813 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 430070 WUHAN, HUBEI PROVINCE TO: 431614 XIAOGAN, HUBEI PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20120813 Address after: 431614 No. 8 Power Plant Road, New River Town, Hubei, Hanchuan Patentee after: Sanjiang Wuhan Aerospace solid Hanchuan biological science and Technology Co., Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: Wuhan University of Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100721 Termination date: 20140929 |
|
| EXPY | Termination of patent right or utility model |