CN103113669A - Method for preparing gradient-controlled porous polymer structure material - Google Patents
Method for preparing gradient-controlled porous polymer structure material Download PDFInfo
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- CN103113669A CN103113669A CN2013100150875A CN201310015087A CN103113669A CN 103113669 A CN103113669 A CN 103113669A CN 2013100150875 A CN2013100150875 A CN 2013100150875A CN 201310015087 A CN201310015087 A CN 201310015087A CN 103113669 A CN103113669 A CN 103113669A
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Abstract
The invention relates to a novel method for preparing a gradient-controlled porous polymer structure material, and in particular relates to a method for preparing a novel gradient-controlled porous high polymer material by utilizing the unique heat flow behavior of the incompatible or partially compatible polymer blend. A gradient double-continuous phase structure with spatial continuous change is obtained by controlling the inner temperature distribution of the polymer blend material, and one of the double continuous phases is etched, so that the gradient porous high polymer material can be obtained. The invention belongs to the technical field of gradient porous high polymer materials.
Description
Technical field
The present invention relates to a kind of novel controlled gradient porous polymer architecture material preparation method, specifically utilize heat flow behavioral study incompatible or part compatible polymeric blend uniqueness to prepare novel controlled gradient porous structure macromolecular material, obtain space continually varying gradient co-continuous phase phase structure by the distribution of controlling the polymer blending material internal temperature, just can obtain the gradient porous structure macromolecular material after the wherein phased soln of co-continuous phase is etched away, belong to gradient porous polymer architecture material technology 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, development along with biotechnology, gradient porous material more and more is widely used at food, medicine and biological field and is filtered and degerming, and can realize efficient, energy-saving and environmental protection, reach the effect of " cold sterilization "; 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. in addition, and is widely used in fields such as beverage, milk-product manufacturing, petrochemical complex, medicine, agricultural chemicals, biotechnology and energy environment protections.
The characteristics of gradient porous material are to have a large amount of pores, and the aperture makes the material of Gradient distribution with scantling, and the shape of pore, content, aperture and distribution thereof have great effect to its performance and function; Research and application about gradient porous material at present mainly is confined to metal, pottery and other inorganic molecules field of compound material, and preparation method also main particle gradient take these materials as object arranges sintering process, plasma spraying method, physical vapor deposition, vapour deposition process and Self-propagating high-temperature method etc.; Yet, report as the gradient function research of the macromolecular material of material important branch is but relatively less, Chinese patent ZL200810209700.6 " method for preparing gradient porous material " discloses a kind of method that adopts foaming forming technique to prepare gradient porous material, success prepare the gradient porous material consistent with the 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 a kind of compression molding that utilizes, the method for preparing gradient porous NiTi alloy by the powder diameter of 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 announced the preparation method of the gradient porous NiTi alloy of cylinder shape, do not studied the preparation method of diamond type gradient porous material.
In the present invention, introducing the temperature field in having the incompatible of co-continuous phase structure or part compatible polymeric blend heat treatment process, utilize the heat flow behavioral study of polymkeric substance uniqueness to prepare novel controlled gradient porous structure macromolecular material, obtain co-continuous phase phase farmland in space continually varying phase structure by the distribution of controlling the polymer blending material internal temperature, just can obtain novel controlled gradient porous structure macromolecular material after the wherein phased soln of co-continuous phase is etched away.
Summary of the invention
The object of the invention is to utilize heat flow behavioral study incompatible or part compatible polymeric blend uniqueness to prepare novel controlled gradient porous structure macromolecular material, when having the blend thermal treatment of co-continuous phase microtexture, obtain space continually varying gradient co-continuous phase phase structure by the distribution of controlling the polymer blending material internal temperature, just can obtain the gradient porous structure macromolecular material after the wherein phased soln of co-continuous phase is etched away.
The aperture of this gradient porous material, the graded in aperture and can regulate by controlling in the melt blending process temperature 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) will 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 control by controlling mixing time, melting temperature, rotating speed the phase size size of co-continuous phase.
2) blend polymer material obtained above is joined in mould, then put it into thermal treatment 10 ~ 120min in the temperature field, rapid cooling sample after handling, and by controlling the graded of temperature and heat treatment time control co-continuous phase size.
3) utilize the dissolution with solvents etching method that the phased soln in above-mentioned blend is etched away, obtain controlled gradient porous polymer architecture material.
described gradient porous polymer matrix material includes but not limited to polypropylene, polyethylene, polystyrene, poly(lactic acid) and polycaprolactone, the co-mixing system that body material and another polymer materials form includes but not limited to polypropylene/ethylene-octene copolymer, Pp/epdm, polypropylene/styrene-ethylene-butylene copolymer, polypropylene/polystyrene, polyethylene/polystyrene, polyethylene/styrene-ethylene-butylene copolymer, 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 ℃, and rotating speed is 30 ~ 80rpm.
Described temperature field can be realized in the following way, and the blend material in mould is applied different temperature two different positions, thereby makes blend material formation temperature field between the two positions; Two different positions of blend material can be upper-lower position, position, left and right or the center of material and surrounding position; High-temperature part is 190 ~ 240 ℃, and low-temp. portion is divided into room temperature ~ 100 ℃, 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-butylene copolymer is tetrahydrofuran (THF), the solvent of dissolved polystyrene is hexanaphthene, tetrahydrofuran (THF) or trichloromethane, the solvent of dissolving polymethylmethacrylate is formic acid, and the solvent of dissolving polycaprolactone is acetic acid.
Description of drawings
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 structured material that obtains in the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the gradient porous polypropylene structured material that obtains in the embodiment of the present invention 2.
Embodiment
Embodiment 1
A) polypropylene (PP), ethene-1-octene copolymer (POE) pellet are successively cleaned with tap water and distilled water, then dry 10h in the vacuum drying oven under 80 ℃ and 50 ℃ respectively.
B) mass ratio by 1:1 takes PP and the POE pellet that gross weight is 50 grams, carries out blend in XXS-30 type Banbury mixer, and melting temperature is 200 ℃, and mixing rotating speed is 40rpm, and mixing time is 10min, prepares the PP/POE blend.
C) the PP/POE polymer blending matter sample with co-continuous phase microtexture with the aforesaid method preparation joins in mould, mould is placed on the hot platform of 200 ℃, the aluminium block compacting of mould top, and to keep upper temp be room temperature, as schematic diagram 1(a) as shown in, because the difference of sample top and bottom temperature of living in can form a temperature field on the sample interior vertical direction, take out sample after thermal treatment 60min and put into frozen water cooling.
D) with the sample after thermal treatment in the n-heptane solution of 60 ℃ after etching 60min, put it in vacuum drying oven, obtain gradient porous polypropylene material after drying, Fig. 2 is the scanning electron microscope (SEM) photograph of the gradient porous polypropylene structured material for preparing 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), ethene-1-octene copolymer (POE) pellet are successively cleaned with tap water and distilled water, then dry 10h in the vacuum drying oven under 80 ℃ and 50 ℃ respectively.
B) mass ratio by 1:1 takes PP and the POE pellet that gross weight is 50 grams, carries out blend in XXS-30 type Banbury mixer, and melting temperature is 200 ℃, and mixing rotating speed is 60rpm, and mixing time is 10min, prepares the PP/POE blend.
C) the PP/POE polymer blending matter sample with co-continuous phase microtexture with the aforesaid method preparation joins in mould, mould is placed on the hot platform of 200 ℃, the aluminium block compacting of mould top, and to keep upper temp be 100 ℃, as schematic diagram 1(a) as shown in, take out sample after thermal treatment 30min and put into frozen water cooling.
D) with the sample after thermal treatment in the n-heptane solution of 60 ℃ after etching 60min, put it in vacuum drying oven, obtain gradient porous polypropylene material after drying, Fig. 3 is the scanning electron microscope (SEM) photograph of the gradient porous polypropylene structured material for preparing 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 are successively cleaned with tap water and distilled water, then dry 8h in the vacuum drying oven under 70 ℃.
B) mass ratio by 1:1 takes PS and the PMMA pellet that gross weight is 50 grams, carries out blend in XXS-30 type Banbury mixer, and melting temperature is 210 ℃, and mixing rotating speed is 50rpm, and mixing time is 6min, prepares the PS/PMMA blend.
C) the PS/PMMA polymer blending matter sample with co-continuous phase microtexture with the aforesaid method preparation joins in mould, mould is placed on the aluminium block that is in room temperature, 200 ℃ of aluminum strips are inserted from sample top, and to keep the aluminum strip temperature be 200 ℃, as schematic diagram 1(b) as shown in, take out sample after thermal treatment 20min and put into frozen water cooling.
D) sample after thermal treatment is put into formic acid solution etching 10d after, put it in vacuum drying oven, obtain gradient porous polystyrene material after drying, the aperture of gradient porous polystyrene material reduces to surrounding gradually from inserting a little of aluminum strip.
Embodiment 4
A) poly(lactic acid) (PLA), polystyrene (PS) are dried 24h respectively in the vacuum drying oven under 70 ℃ and room temperature.
B) mass ratio by 50:50 takes PLA and the PS pellet that gross weight is 50 grams, carries out blend in XXS-30 type Banbury mixer, and melting temperature is 220 ℃, and mixing rotating speed is 60rpm, and mixing time is 10min, prepares the PLA/PS blend.
C) the PLA/PS polymer blending matter sample with co-continuous phase microtexture with the aforesaid method preparation joins in mould, mould is placed on the hot platform of 200 ℃, the aluminium block compacting of mould top, and to keep upper temp be room temperature, as schematic diagram 1(a) as shown in, take out sample after thermal treatment 30min and put into frozen water cooling.
D) sample after thermal treatment is put into the cyclohexane solution etching 7d of 60 ℃ after, put it in vacuum drying oven, obtain gradient porous poly-lactic acid material after drying, the high-temperature part of the aperture of gradient porous poly-lactic acid material during from thermal treatment reduces gradually to the low temperature part.
Claims (5)
1. a controlled gradient porous polymer architecture material preparation method, is characterized in that comprising the steps:
1) will 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 control by controlling mixing time, melting temperature, rotating speed the phase size size of co-continuous phase;
2) blend polymer material obtained above is joined in mould, then put it into thermal treatment 10 ~ 120min in the temperature field, rapid cooling sample after handling, and by controlling the graded of temperature and heat treatment time control co-continuous phase size;
3) utilize the dissolution with solvents etching method that the phased soln in above-mentioned blend is etched away, obtain controlled gradient porous polymer architecture material.
2. a kind of controlled gradient porous polymer architecture material preparation method 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 that body material and another polymer materials form includes but not limited to polypropylene/ethylene-octene copolymer, Pp/epdm, polypropylene/styrene-ethylene-butylene copolymer, polypropylene/polystyrene, polyethylene/polystyrene, polyethylene/styrene-ethylene-butylene copolymer, polystyrene/polymethylmethacrylate, poly(lactic acid)/polystyrene, polylactic acid and caprolactone and polycaprolactone/polystyrene.
3. a kind of controlled gradient porous polymer architecture material preparation method 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 ℃, and rotating speed is 30 ~ 80rpm.
4. a kind of controlled gradient porous polymer architecture material preparation method as claimed in claim 1, it is characterized in that: described temperature field can be realized in the following way, blend material in mould is applied different temperature two different positions, thereby make blend material formation temperature field between the two positions; Two different positions of blend material can be upper-lower position, position, left and right or the center of material and surrounding position; High-temperature part is 190 ~ 240 ℃, and low-temp. portion is divided into room temperature ~ 100 ℃.
5. a kind of controlled gradient porous polymer architecture material preparation method 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-butylene copolymer is tetrahydrofuran (THF), the solvent of dissolved polystyrene is hexanaphthene, tetrahydrofuran (THF) or trichloromethane, the solvent of dissolving polymethylmethacrylate is formic acid, and the solvent of dissolving polycaprolactone is acetic acid.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629078A (en) * | 2015-02-02 | 2015-05-20 | 四川大学 | Preparation method of gradient porous polymer material |
| CN105906835A (en) * | 2016-07-06 | 2016-08-31 | 东南大学 | Preparation method of biological material with gradient changed pores |
| CN106363860A (en) * | 2016-08-25 | 2017-02-01 | 河南理工大学 | Non-equilibrium injection molding method for high-molecular-based gradient material |
| CN107130133A (en) * | 2017-05-26 | 2017-09-05 | 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 |
| CN107312245A (en) * | 2017-08-07 | 2017-11-03 | 菏泽学院 | Gradient foaming polypropylene sheet and preparation method thereof |
| CN108795052A (en) * | 2018-07-03 | 2018-11-13 | 四川大学 | Rubbery foam and preparation method thereof with gradient foam structure |
| 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 |
| CN112382722A (en) * | 2020-11-02 | 2021-02-19 | 南京工业大学 | Nonvolatile resistive random access memory with adjustable writing voltage and preparation method thereof |
| CN113426497A (en) * | 2021-06-02 | 2021-09-24 | 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 |
| CN115537001A (en) * | 2022-09-27 | 2022-12-30 | 常州大学 | Polylactic acid-based hierarchical porous material and phase separation preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418391A (en) * | 2008-12-15 | 2009-04-29 | 哈尔滨理工大学 | Method for preparing gradient porous material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101418391A (en) * | 2008-12-15 | 2009-04-29 | 哈尔滨理工大学 | Method for preparing gradient porous material |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629078A (en) * | 2015-02-02 | 2015-05-20 | 四川大学 | Preparation method of gradient porous polymer material |
| CN105906835A (en) * | 2016-07-06 | 2016-08-31 | 东南大学 | Preparation method of biological material with gradient changed pores |
| CN106363860A (en) * | 2016-08-25 | 2017-02-01 | 河南理工大学 | Non-equilibrium injection molding method for high-molecular-based gradient material |
| 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 |
| CN107130133A (en) * | 2017-05-26 | 2017-09-05 | 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 |
| CN107312245A (en) * | 2017-08-07 | 2017-11-03 | 菏泽学院 | Gradient foaming polypropylene sheet and preparation method thereof |
| CN108795052A (en) * | 2018-07-03 | 2018-11-13 | 四川大学 | Rubbery foam and preparation method thereof with gradient foam structure |
| 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 |
| CN112382722A (en) * | 2020-11-02 | 2021-02-19 | 南京工业大学 | Nonvolatile resistive random access memory with adjustable writing voltage and preparation method thereof |
| CN113426497A (en) * | 2021-06-02 | 2021-09-24 | 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 |
| CN115537001A (en) * | 2022-09-27 | 2022-12-30 | 常州大学 | Polylactic acid-based hierarchical porous material and phase separation preparation method thereof |
| CN115537001B (en) * | 2022-09-27 | 2024-04-26 | 常州大学 | Polylactic acid-based hierarchical porous material and phase separation preparation method thereof |
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