CN104530672A - Method for preparing silicon-containing micron-fiber-toughened PHBV composite material - Google Patents
Method for preparing silicon-containing micron-fiber-toughened PHBV composite material Download PDFInfo
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- CN104530672A CN104530672A CN201510021973.8A CN201510021973A CN104530672A CN 104530672 A CN104530672 A CN 104530672A CN 201510021973 A CN201510021973 A CN 201510021973A CN 104530672 A CN104530672 A CN 104530672A
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Abstract
The invention discloses a method for preparing a silicon-containing micron-fiber-toughened PHBV composite material and belongs to the field of natural polymer material-toughened biodegradable plastics. The method comprises the following steps of dispersing a silicon-containing raw material in an aqueous sodium of sodium hydroxide with mass fraction of 10-35%, holding the temperature in a temperature range of 20-40 DEG C for 4-8 hours, diluting, filtering, adding 1-5% of a dispersant, carrying out low-pressure crushing by a homogenizing apparatus at a homogenizing pressure of 100-200bar, cycling for 6-15 times, separating and carrying out vacuum drying treatment to obtain silicon-containing micron-fiber; carrying out melt blending on silicon-containing micron-fiber, poly(beta-hydroxybutyrate-beta-hydroxyvalerate) (PHBV) at a mass ratio of (1:10)-(1:25), carrying out extrusion molding and granulating to prepare the silicon-containing micron-fiber-toughened PHBV composite material. By the method, when PHBV is toughened by virtue of the plant fiber in the prior art, the problems that the plant fiber needs to be prepared into nanoscale, a large amount of chemicals and power are consumed and the process is complex can be solved. According to the method for preparing the composite material, the agricultural residues can be utilized and thus the environment friendliness is achieved.
Description
Technical field
The present invention relates to the preparation method of the toughness reinforcing PHBV matrix material of a kind of siliceous micrometer fibers, belong to the toughness reinforcing biodegradable plastic field of natural macromolecular material.
Background technology
Along with petroleum resources worsening shortages and " white pollution " increase the weight of, the plastics utilizing biological polymer to carry out petroleum replacing synthesis have become the focus paid close attention in the whole world.Poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) has many good characteristics such as biodegradability, biocompatibility, piezoelectricity, optical activity, has wide practical use in fields such as surgical stapling, degradable package material, agricultural mulchings.Polymer materials in actual use, not only needs to have higher intensity, but also should have higher toughness, especially when being used as structured material.PHBV is a kind of polyester of isotactic crystallinity, is similar to polypropylene (PP) or polyethylene terephthalate (PET).The degree of crystallinity of PHBV is up to 80%, and elongation at break is about 3.0%, is only 1/20 of 1/8 ~ 1/9, PET of PP; Under normal temperature and second-order transition temperature (4 DEG C), show as great fragility, impact resistance is poor, easily cracked, limits its Application Areas, hinders its large-scale commercialization and uses.
In order to improve the toughness of PHBV, the methods such as elastomerics, phenolic compound, reactive toughening, super-high relative molecular weight polyoxyethylene glycol are usually adopted to carry out toughening modifying.The toughner adopted is better flexible, but mostly is non-degradable material, produces certain negative impact to the biological degradability of material.Find complete biodegradable, there is good toughening effect properties-correcting agent still significant.Lignocellulosic fiber source extensively, there is certain intensity, biocompatibility and biodegradable, become the extremely potential material of the one improving PHBV performance gradually.At present, adopt vegetable fibre to improve the toughness of PHBV, usually need vegetable fibre to make Nano grade, the chemical agent that this process need consumption is a large amount of and power, and complex procedures.
Adopt nano silicon also can carry out toughening modifying to PHBV.In PHBV crystallisation process, nano silicon plays the effect of heterogeneous nucleation agent, improves crystallization rate, reduces spherulite size.Result of study shows, and when the addition of nano silicon is 0.1 ~ 0.5% time, the tension fracture elongation rate of PHBV improves, and shock strength obviously increases, and Young's modulus then remains unchanged substantially.Because nano silicon density is low, specific surface area is large, hole is abundant, when addition is more than 0.5%, easily reunite in PHBV, increase the difficulty of processing of material.
The vegetable fibre that rice straw etc. are rich in silicon matter is rich in micro-nano-silica by biomineralization at its outside surface, these silicon matters often have a negative impact to the final performance of material in the preparation process of material, therefore need to adopt chemistry, physics, the method such as biological removes silicon matter, but pretreated effect is often limited, and silicon matter is still retained in plant fibre surface after the pre-treatment largely.Therefore, how to utilize the silicon matter of plant fibre surface, in the preparation process of material, make it turn waste into wealth becomes one of difficult point of such vegetable fibre utilization.
Summary of the invention
The object of the present invention is to provide the method for the toughness reinforcing PHBV of a kind of siliceous micrometer fibers.Vegetable fibre is made Nano grade by needing of existing when the method overcoming the toughness reinforcing PHBV of existing vegetable fibre, consume the deficiency of a large amount of chemical agent and power, utilize silicon matter in vegetable fibre sepn process to be attached to fiber surface simultaneously, its size modes still remains on micro-nano rank, has toughening effect to PHBV.The method prepares simple and fast, is easy to control, and power consumption is few, can be used for industrialized mass production.
Technical solution of the present invention: siliceous fibrous material is dispersed in the aqueous sodium hydroxide solution of low concentration, in certain temperature range, keep for some time, be conducive to the removal of lipoid material, hemicellulose and the slippage of cellulose molecular chain in siliceous vegetable fibre; Then above-mentioned blend passed through dilution, filter, a certain amount of dispersion agent is added in the throw out obtained, overcome fibrous material to be connected and the wadding caused gathers phenomenon owing to producing hydrogen bond between hydroxyl with hydroxyl in micronized process, then homogeneous instrument is adopted to carry out low pressure fragmentation, obtain siliceous micrometer fibers blend, siliceous micrometer fibers blend is separated, remove water-dispersion phase, then carry out vacuum-treat, obtain siliceous micrometer fibers.Finally, siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) are carried out melt blending, through extrusion granulating, makes the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.
The concrete preparation method of a kind of siliceous micrometer fibers toughness reinforcing PHBV matrix material is as follows:
(1) siliceous fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution of 10 ~ 35%, the mass ratio of described siliceous fibrous material and aqueous sodium hydroxide solution is 1: 10 ~ 1: 30, under 20 ~ 40 DEG C of temperature ranges, keep 4 ~ 8h, obtain the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filtration, dispersion agent 1 ~ 5% is added in the throw out obtained, then homogeneous instrument is utilized to carry out low pressure fragmentation, homogenization pressure is 100 ~ 200bar, cycle index is 6 ~ 15 times, obtain siliceous micrometer fibers blend, finally carry out being separated, vacuum drying treatment, obtain siliceous micrometer fibers.
(2) by siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 10 ~ 1: 25, carry out melt blending, processing temperature is 160 ~ 185 DEG C, screw speed is 10 ~ 25r/min, blended time 2.5 ~ 6min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.
Advantage of the present invention: the raw material that the present invention adopts is the vegetable fibre being rich in silicon matter, wide material sources are cheap.Adopt the siliceous fibrous material of NaOH pretreatment of low concentration, effectively can retain the silicon matter in vegetable fibre on the one hand, be conducive to lipoid material in cellulose molecular chain, the removal of hemicellulose and the slippage of cellulose molecular chain on the other hand; Then adopt low pressure to carry out mechanical shearing to material, destroy the gathering of fiber, make its fibrillation, the siliceous micrometer fibers size of preparation is at 2 ~ 10 μm and be evenly distributed.In addition, before low pressure fragmentation, add dispersion agent, fibrous material can be overcome and to be connected and the wadding caused gathers phenomenon owing to producing hydrogen bond between hydroxyl with hydroxyl in micronized process, increase the follow-up toughening effect to PHBV simultaneously.
Performance test shows: with the PHBV matrix material that siliceous micrometer fibers is toughness reinforcing, its tension fracture elongation rate adds 84.33%, and shock strength adds 55%.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope diagram of siliceous micrometer fibers in embodiment 1.
Embodiment
Embodiment 1, siliceous for 1g fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution 10g of 10%, keeps 8h at 20 DEG C, obtains the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filtration, in the throw out of gained, add the polyoxyethylene glycol of 1%, then adopt homogeneous instrument to carry out low pressure fragmentation, cracking pressure 100bar, cycle index 15 times, obtains siliceous micrometer fibers blend, obtains siliceous micrometer fibers through separation, vacuum-drying.By obtained siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 25, carry out melt blending, processing temperature is 175 DEG C, screw speed is 10r/min, blended time 2.5min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.After tested, the PHBV matrix material tension fracture elongation rate prepared adds 84.33%, and shock strength adds 55%.
Embodiment 2, siliceous for 2g fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution 40g of 35%, keeps 6h at 30 DEG C, obtains the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filtration, in the throw out of gained, add the polyoxyethylene glycol of 3%, then adopt homogeneous instrument to carry out low pressure fragmentation, cracking pressure 150bar, cycle index obtains siliceous micrometer fibers blend for 10 times, obtains siliceous micrometer fibers through separation, vacuum-drying.By obtained siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 15, carry out melt blending, processing temperature is 185 DEG C, screw speed is 15r/min, blended time 3.5min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.After tested, the PHBV matrix material tension fracture elongation rate prepared adds 48.1%, and shock strength adds 32.1%.
Embodiment 3, siliceous for 2g fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution 25g of 20%, keeps 6h at 30 DEG C, obtains the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filtration, in the throw out of gained, add the polyoxyethylene glycol of 5%, then adopt homogeneous instrument to carry out low pressure fragmentation, cracking pressure 200bar, cycle index 6 times, obtains siliceous micrometer fibers blend, obtains siliceous micrometer fibers through separation, vacuum-drying.By obtained siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 10, carry out melt blending, processing temperature is 185 DEG C, screw speed is 20r/min, blended time 5min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.After tested, the PHBV matrix material tension fracture elongation rate prepared adds 77.8%, and shock strength adds 40.3%.
Embodiment 4, siliceous for 1g fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution 30g of 25%, keeps 4h at 40 DEG C, obtains the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filtration, in the throw out of gained, add the polyoxyethylene glycol of 3%, then adopt homogeneous instrument to carry out low pressure fragmentation, cracking pressure 150bar, cycle index 8 times, obtains siliceous micrometer fibers blend, obtains siliceous micrometer fibers through separation, vacuum-drying.By obtained siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 20, carry out melt blending, processing temperature is 160 DEG C, screw speed is 25r/min, blended time 6min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.After tested, the PHBV matrix material tension fracture elongation rate prepared adds 66.7%, and shock strength adds 46.1%.
Claims (5)
1. a preparation method for the toughness reinforcing PHBV matrix material of siliceous micrometer fibers, is characterized in that obtaining as follows:
(1) siliceous fibrous material being dispersed in massfraction is in the aqueous sodium hydroxide solution of 10 ~ 35%, the mass ratio of described siliceous fibrous material and aqueous sodium hydroxide solution is 1: 10 ~ 1: 30, under 20 ~ 40 DEG C of temperature ranges, keep 4 ~ 8h, obtain the blend containing silica fibre and aqueous sodium hydroxide solution; By above-mentioned blend through dilution, filter, in the throw out obtained, add dispersion agent, then utilize homogeneous instrument to carry out low pressure fragmentation, obtain siliceous micrometer fibers blend, finally carry out being separated, vacuum-drying, obtain siliceous micrometer fibers.
(2) by siliceous micrometer fibers, poly-(beta-hydroxy-butanoic acid ester-beta-hydroxy valerate) (PHBV) in mass ratio 1: 10 ~ 1: 25, carry out melt blending, processing temperature is 160 ~ 185 DEG C, screw speed is 10 ~ 25r/min, blended time 2.5 ~ 6min, through extrusion granulating, make the toughness reinforcing PHBV matrix material of siliceous micrometer fibers.
2. the preparation method of the toughness reinforcing PHBV matrix material of siliceous micrometer fibers according to claim 1, is characterized in that described siliceous fibrous material comprises the vegetable fibre that rice straw, wheat straw, reed etc. are rich in silicon matter.
3. the preparation method of the toughness reinforcing PHBV matrix material of siliceous micrometer fibers according to claim 1, is characterized in that described siliceous micron fiber diameter is 2 ~ 10 microns.
4. the preparation method of the toughness reinforcing PHBV matrix material of siliceous micrometer fibers according to claim 1, it is characterized in that described dispersion agent is polyoxyethylene glycol, the quality of dispersion agent is 1 ~ 5% of siliceous fibrous material.
5. the preparation method of the toughness reinforcing PHBV matrix material of siliceous micrometer fibers according to claim 1, it is characterized in that pressure used in described low pressure shattering process is 100 ~ 200bar, cycle index is 6 ~ 15 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245232A (en) * | 2017-07-10 | 2017-10-13 | 东莞市联洲知识产权运营管理有限公司 | A kind of PHBV composites being modified based on bacteria cellulose |
| CN113248768A (en) * | 2021-05-10 | 2021-08-13 | 宁波大学 | Toughening treatment method of PHBV product |
| CN118003608A (en) * | 2024-03-04 | 2024-05-10 | 保定市富新包装有限公司 | Preparation method for improving compression resistance of environment-friendly packaging material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MAURIZIO AVELLA ET.AL: "Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-Based Biocomposites Reinforced with Kenaf Fibers", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 徐山青: "Henequen 纤维/PHBV 树脂可生物降解复合材料界面粘结性能的研究", 《产业用纺织品》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245232A (en) * | 2017-07-10 | 2017-10-13 | 东莞市联洲知识产权运营管理有限公司 | A kind of PHBV composites being modified based on bacteria cellulose |
| CN113248768A (en) * | 2021-05-10 | 2021-08-13 | 宁波大学 | Toughening treatment method of PHBV product |
| CN118003608A (en) * | 2024-03-04 | 2024-05-10 | 保定市富新包装有限公司 | Preparation method for improving compression resistance of environment-friendly packaging material |
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