CN103113669B - A kind of preparation method of gradient-controllable porous polymer structured material - Google Patents
A kind of preparation method of gradient-controllable porous polymer structured material Download PDFInfo
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- CN103113669B CN103113669B CN201310015087.5A CN201310015087A CN103113669B CN 103113669 B CN103113669 B CN 103113669B CN 201310015087 A CN201310015087 A CN 201310015087A CN 103113669 B CN103113669 B CN 103113669B
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Abstract
The present invention relates to a kind of preparation method of novel gradient-controllable porous polymer structured material, heat flow behavioral study that is incompatible or partially compatible blend polymer uniqueness is specifically utilized to prepare novel gradient-controllable vesicular structure macromolecular material, the gradient two-arch tunnel structure of Spatial continual change is obtained by the distribution controlling polymer blending material internal temperature, a wherein phased soln of two-arch tunnel just can be obtained gradient porous structure macromolecular material after etching away, belong to gradient porous polymer construction material technical field.
Description
Technical field
The present invention relates to a kind of preparation method of novel gradient-controllable porous polymer structured material, heat flow behavioral study that is incompatible or partially compatible blend polymer uniqueness is specifically utilized to prepare novel gradient-controllable vesicular structure macromolecular material, the gradient two-arch tunnel phase structure of Spatial continual change is obtained by the distribution controlling polymer blending material internal temperature, a wherein phased soln of two-arch tunnel just can be obtained gradient porous structure macromolecular material after etching away, belong to gradient porous polymer construction material technical field.
Background technology
Gradient porous material is as the integral part of function-graded material, be widely applied in people's daily life, production and defence and military, and, along with the development of biotechnology, gradient porous material food, medicine and biological field be more and more widely used in filter and degerming, and efficient, energy-saving and environmental protection can be realized, reach the effect of " cold sterilization "; In addition gradient porous material also can be used for thermal insulation material, piezoelectric, porous electrode, sound-absorbing material, energy-absorbing shielding, catalyst separating and regeneration, combustion chamber and strainer etc., and is widely used in fields such as beverage, milk-product manufacture, petrochemical complex, medicine, agricultural chemicals, biotechnology and energy environment protections.
The feature of gradient porous material has a large amount of pore, and the material of Gradient distribution is made with scantling in aperture, and the shape of pore, content, aperture and distribution thereof have great effect to its performance and function; At present about the investigation and application of gradient porous material is mainly limited to metal, pottery and other inorganic molecules field of compound material, the preparation method also main particle gradient being object with these materials arranges sintering process, plasma spraying method, physical vapor deposition, vapour deposition process and Self-propagating high-temperature method etc.; But, the report studied as the gradient functionization of the macromolecular material of material important branch is but relatively less, Chinese patent ZL200810209700.6 " prepares the method for gradient porous material " and discloses a kind of method adopting foaming forming technique to prepare gradient porous material, successfully prepare the gradient porous material consistent with skeleton structure, but, need to use pore-creating agent in the preparation process of these class methods, and the gradient number of plies of preparation is limited; Chinese patent ZL201010104527.0 " a kind of preparation method of super-elastic gradient porous NiTi alloy " discloses one and utilizes compression molding, the method of gradient porous NiTi alloy is prepared by the powder diameter adjusting every one deck, successfully prepare the gradient porous NiTi alloy consistent with organization of human body, but the porosity of the titanium alloy that these class methods are prepared is very low, and only disclose the preparation method of the gradient porous NiTi alloy of cylinder shape, the not preparation method of research diamond type gradient porous material.
In the present invention, temperature field is being introduced to having in the incompatible of two-arch tunnel structure or partially compatible blend polymer heat treatment process, the heat flow behavioral study of polymkeric substance uniqueness is utilized to prepare novel gradient-controllable vesicular structure macromolecular material, obtain by the distribution controlling polymer blending material internal temperature the phase structure that two-arch tunnel phase domain changes at Spatial continual, a wherein phased soln of two-arch tunnel just can be obtained novel gradient-controllable vesicular structure macromolecular material after etching away.
Summary of the invention
The object of the invention is to utilize heat flow behavioral study that is incompatible or partially compatible blend polymer uniqueness to prepare novel gradient-controllable vesicular structure macromolecular material, to when there is the blend thermal treatment of two-arch tunnel microtexture, obtained the gradient two-arch tunnel phase structure of Spatial continual change by the distribution controlling polymer blending material internal temperature, a wherein phased soln of two-arch tunnel just can be obtained gradient porous structure macromolecular material after etching away.
The aperture of this gradient porous material, the graded in aperture and regulate by the temperature controlled in melt blending process in processing conditions (mixing time, melting temperature, rotating speed etc.) and heat treatment process, preparation method's concrete steps of the present invention are as follows:
1) by draw up standby gradient porous polymer matrix material and another polymer materials in mass ratio 1:1 prepare blend polymer by forcing machine or Banbury mixer melt blending, and can by the phase size size controlling mixing time, melting temperature, rotating speed control two-arch tunnel.
2) blend polymer material obtained above is joined in mould, then put it into thermal treatment 10 ~ 120min in temperature field, after processing, cool sample rapidly, and control the graded of two-arch tunnel size by control temperature and heat treatment time.
3) utilize dissolution with solvents etching method to be etched away by the phased soln in above-mentioned blend, obtain gradient-controllable porous polymer structured material.
Described gradient porous polymer matrix material includes but not limited to polypropylene, polyethylene, polystyrene, poly(lactic acid) and polycaprolactone, the co-mixing system of body material and another polymer materials composition includes but not limited to polypropylene/ethylene-octene copolymer, Pp/epdm, polypropylene/styrene-ethylene-butadiene multipolymer, polypropylene/polystyrene, polyethylene/polystyrene, polyethylene/styrene-ethylene-butadiene multipolymer, polystyrene/polymethylmethacrylate, poly(lactic acid)/polystyrene, polylactic acid and caprolactone and polycaprolactone/polystyrene.
In described melt blending, mixing time is 5 ~ 20 minutes, and melting temperature is 190 ~ 240 DEG C, and rotating speed is 30 ~ 80rpm.
Described temperature field realizes by such as under type, applies different temperature, thus make blend material formation temperature field between the two positions to the blend material in mould two different positions; The different position of blend material two can be the upper-lower position of material, right position or center and surrounding position; High-temperature part is 190 ~ 240 DEG C, and low-temp. portion is divided into room temperature ~ 100 DEG C, and heat treatment time is 10 ~ 120min.
Described solvent is different for dissolving different polymkeric substance, the solvent of dissolve ethylene-octene copolymer is normal heptane, the solvent of dissolving terpolymer EP rubber, styrene-ethylene-butadiene multipolymer is tetrahydrofuran (THF), the solvent of dissolved polystyrene is hexanaphthene, tetrahydrofuran (THF) or trichloromethane, the solvent dissolving polymethylmethacrylate is formic acid, and the solvent dissolving polycaprolactone is acetic acid.
Accompanying drawing explanation
Fig. 1 is the temperature field schematic diagram that the present invention builds;
Fig. 2 is the scanning electron microscope (SEM) photograph of the gradient porous Polypropylene structural material obtained in the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the gradient porous Polypropylene structural material obtained in the embodiment of the present invention 2.
Embodiment
embodiment 1
A) polypropylene (PP), ethylene-l-octane copolymer (POE) pellet priority tap water and distilled water are cleaned, in the vacuum drying oven then respectively at 80 DEG C and 50 DEG C, dry 10h.
B) take by the mass ratio of 1:1 PP and the POE pellet that gross weight is 50 grams, carry out blended in XXS-30 type Banbury mixer, melting temperature is 200 DEG C, and mixing rotating speed is 40rpm, and mixing time is 10min, prepares PP/POE blend.
C) the PP/POE polymer blending matter sample with two-arch tunnel microtexture prepared by aforesaid method joins in mould, mould is placed in the thermal station of 200 DEG C, mould upstream aluminium block compacting, and to maintain upper temp be room temperature, as schematic diagram 1(a) shown in, residing for sample top and bottom, the difference of temperature can form a temperature field in sample interior vertical direction, takes out sample and put into frozen water to cool after thermal treatment 60min.
D) after the sample after thermal treatment being etched 60min in the n-heptane solution of 60 DEG C, put it in vacuum drying oven, gradient porous polypropylene material is obtained after drying, Fig. 2 is the scanning electron microscope (SEM) photograph of the gradient porous Polypropylene structural material prepared in the present embodiment, as can be seen from the figure, the aperture of porous polypropylene material reduces from left to right gradually.
embodiment 2
A) polypropylene (PP), ethylene-l-octane copolymer (POE) pellet priority tap water and distilled water are cleaned, in the vacuum drying oven then respectively at 80 DEG C and 50 DEG C, dry 10h.
B) take by the mass ratio of 1:1 PP and the POE pellet that gross weight is 50 grams, carry out blended in XXS-30 type Banbury mixer, melting temperature is 200 DEG C, and mixing rotating speed is 60rpm, and mixing time is 10min, prepares PP/POE blend.
C) the PP/POE polymer blending matter sample with two-arch tunnel microtexture prepared by aforesaid method joins in mould, mould is placed in the thermal station of 200 DEG C, mould upstream aluminium block compacting, and to maintain upper temp be 100 DEG C, as schematic diagram 1(a) shown in, take out sample after thermal treatment 30min and put into frozen water and cool.
D) after the sample after thermal treatment being etched 60min in the n-heptane solution of 60 DEG C, put it in vacuum drying oven, gradient porous polypropylene material is obtained after drying, Fig. 3 is the scanning electron microscope (SEM) photograph of the gradient porous Polypropylene structural material prepared in the present embodiment, as can be seen from the figure, the aperture of porous polypropylene material increases from left to right gradually.
embodiment 3
A) polystyrene (PS), polymethylmethacrylate (PMMA) pellet priority tap water and distilled water are cleaned, in the vacuum drying oven then at 70 DEG C, dry 8h.
B) take by the mass ratio of 1:1 PS and the PMMA pellet that gross weight is 50 grams, carry out blended in XXS-30 type Banbury mixer, melting temperature is 210 DEG C, and mixing rotating speed is 50rpm, and mixing time is 6min, prepares PS/PMMA blend.
C) the PS/PMMA polymer blending matter sample with two-arch tunnel microtexture prepared by aforesaid method joins in mould, being placed on by mould is on the aluminium block of room temperature, 200 DEG C of aluminum strips are inserted from sample top, and to maintain aluminum strip temperature be 200 DEG C, as schematic diagram 1(b) shown in, take out sample after thermal treatment 20min and put into frozen water and cool.
D) put into by the sample after thermal treatment after formic acid solution etches 10d, put it in vacuum drying oven, obtain gradient porous polystyrene material after drying, the aperture of gradient porous polystyrene material a little reduces to surrounding gradually from inserting of aluminum strip.
embodiment 4
A) poly(lactic acid) (PLA), polystyrene (PS) are dried 24h respectively in the vacuum drying oven under 70 DEG C and room temperature.
B) take by the mass ratio of 50:50 PLA and the PS pellet that gross weight is 50 grams, carry out blended in XXS-30 type Banbury mixer, melting temperature is 220 DEG C, and mixing rotating speed is 60rpm, and mixing time is 10min, prepares PLA/PS blend.
C) the PLA/PS polymer blending matter sample with two-arch tunnel microtexture prepared by aforesaid method joins in mould, mould is placed in the thermal station of 200 DEG C, mould upstream aluminium block compacting, and to maintain upper temp be room temperature, as schematic diagram 1(a) shown in, take out sample after thermal treatment 30min and put into frozen water and cool.
D) after the cyclohexane solution sample after thermal treatment being put into 60 DEG C etches 7d, put it in vacuum drying oven, obtain gradient porous poly-lactic acid material after drying, the aperture of gradient porous poly-lactic acid material reduces from high-temperature part during thermal treatment gradually to low temperature part.
Claims (4)
1. a preparation method for gradient-controllable porous polymer structured material, is characterized in that comprising the steps:
1) by draw up standby gradient porous polymer matrix material and another polymer materials in mass ratio 1:1 prepare blend polymer by forcing machine or Banbury mixer melt blending, and by the phase size size controlling mixing time, melting temperature, rotating speed control two-arch tunnel;
2) blend polymer material obtained above is joined in mould, then put it into thermal treatment 10 ~ 120min in temperature field, after processing, cool sample rapidly, and control the graded of two-arch tunnel size by control temperature and heat treatment time;
3) utilize dissolution with solvents etching method to be etched away by the phased soln in above-mentioned blend, obtain gradient-controllable porous polymer structured material;
Described temperature field realizes in the following way, applies different temperature, thus make blend material formation temperature field between the two positions to the blend material in mould two different positions; The different position of blend material two is the upper-lower position of material, right position or center and surrounding position; High-temperature part is 190 ~ 240 DEG C, and low-temp. portion is divided into room temperature ~ 100 DEG C.
2. the preparation method of a kind of gradient-controllable porous polymer structured material as claimed in claim 1, it is characterized in that: described gradient porous polymer matrix material includes but not limited to polypropylene, polyethylene, polystyrene, poly(lactic acid) and polycaprolactone, the co-mixing system of body material and another polymer materials composition includes but not limited to polypropylene/ethylene-octene copolymer, Pp/epdm, polypropylene/styrene-ethylene-butadiene multipolymer, polypropylene/polystyrene, polyethylene/polystyrene, polyethylene/styrene-ethylene-butadiene multipolymer, polystyrene/polymethylmethacrylate, poly(lactic acid)/polystyrene, polylactic acid and caprolactone and polycaprolactone/polystyrene.
3. the preparation method of a kind of gradient-controllable porous polymer structured material as claimed in claim 1, it is characterized in that: in described melt blending, mixing time is 5 ~ 20 minutes, and melting temperature is 190 ~ 240 DEG C, and rotating speed is 30 ~ 80rpm.
4. the preparation method of a kind of gradient-controllable porous polymer structured material as claimed in claim 1, it is characterized in that: described solvent is different for dissolving different polymkeric substance, the solvent of dissolve ethylene-octene copolymer is normal heptane, the solvent of dissolving terpolymer EP rubber, styrene-ethylene-butadiene multipolymer is tetrahydrofuran (THF), the solvent of dissolved polystyrene is hexanaphthene, tetrahydrofuran (THF) or trichloromethane, the solvent dissolving polymethylmethacrylate is formic acid, and the solvent dissolving polycaprolactone is acetic acid.
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| CN104629078B (en) * | 2015-02-02 | 2017-11-07 | 四川大学 | A kind of preparation method of gradient porous polymeric material |
| CN105906835A (en) * | 2016-07-06 | 2016-08-31 | 东南大学 | Preparation method of biological material with gradient changed pores |
| CN106363860B (en) * | 2016-08-25 | 2019-10-29 | 河南理工大学 | A kind of non-equilibrium injection forming method of polymer-based functionally gradient material (FGM) |
| CN107130133B (en) * | 2017-05-26 | 2019-02-05 | 哈尔滨工业大学 | A kind of ceramic/metal composite materials of gradient bicontinuous structure with and its preparation method and application |
| CN107312237A (en) * | 2017-07-31 | 2017-11-03 | 湖南沃美新材料科技有限公司 | A kind of gradient porosity packaging material and preparation method thereof |
| CN107312245B (en) * | 2017-08-07 | 2019-06-14 | 菏泽学院 | Gradient foaming polypropylene sheet and preparation method thereof |
| CN108795052B (en) * | 2018-07-03 | 2020-12-01 | 四川大学 | Rubber foam material with gradient cell structure and preparation method thereof |
| CN110218423A (en) * | 2019-06-03 | 2019-09-10 | 东华镜月（苏州）纺织技术研究有限公司 | A kind of three-dimensional porous compound Monolithic Columns of polylactic acid and caprolactone and preparation method thereof |
| CN112382722B (en) * | 2020-11-02 | 2023-05-23 | 南京工业大学 | Nonvolatile resistive random access memory with adjustable writing voltage and preparation method thereof |
| CN113426497B (en) * | 2021-06-02 | 2022-07-12 | 广州大学 | Method for manufacturing micro-fluidic chip |
| CN114683460A (en) * | 2022-04-21 | 2022-07-01 | 中国人民解放军军事科学院国防工程研究院 | Preparation method of functionally gradient polyolefin sheet material |
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