CN103435836B - Preparation method of polymer foam material in open pore structure - Google Patents
Preparation method of polymer foam material in open pore structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a polymer foam material in an open pore structure. The preparation method comprises the steps of blending two or more polymers by a melt blending method to form a blend of the polymer, preparing a green body in a definite shape by vacuum mold pressing, putting the green body in a high-pressure reaction kettle, supplying gas, rising temperature and pressure above a supercritical point of the gas to allow the gas to be converted to supercritical fluid, allowing the green body of the blend of the polymers to be foamed by a quick pressure reduction method after the supercritical fluid is saturated in the green body, immersing an obtained polymer foaming material in an appropriate etchant, allowing the etchant and the polymer foaming material to perform physical or chemical reaction, allowing at least one polymer in the polymer foaming material to be dissolved or degraded so as to form channels connecting cells in cell walls, taking out after a certain time, and obtaining the polymer foam material in the open pore structure.
Description
Technical field
The invention belongs to polymer foams field, be for existing open-cell foam materials field provides a kind of new preparation process in particular, namely there is the preparation method of the polymer foams of open-celled structure.
Background technology
Open cell polymer foams, refers to and is interconnected between the abscess in foam, the gas phase in foam and polymkeric substance are all the foam materialss of external phase.Because the foam structure in polymeric matrix is open, be interconnected between abscess, complicated passage can be formed, allow micro-molecular gas or fluid be flowed by material.If size and the form of abscess in open-cell foam materials accurately can be controlled, just can determine the particle size through material, make it play centrifugation.Open cell polymer foams can as separation and sorbing material, support of the catalyst, Thermosensitive Material Used for Controlled Releasing of Medicine, liquid separation mould material, advanced low-k materials etc.
The common preparation method of open cell polymer foams has three kinds: phase separation method, radiation exposure method, stretching method.Phase separation method is that the above mixture system of two-phase or two-phase (polymkeric substance, additive and solvent) produces phase-splitting under the effect such as temperature or solvent, thus in polymeric matrix, forming the method for specific microvoid structure, prepared material can be perforate or unicellular structure.But its main drawback needs to use a large amount of expensive, harmful solvent, and production process is very complicated.The charged particle irradiate base material that radiation exposure method utilizes nuclear reactor to produce, charged particle penetrates film and leaves a trace, and then film is placed in chemical reagent and corrodes, and can obtain microporous membrane, and the hole on film is straight circular hole mostly.Within 1972, the U.S. adopts stretching method to produce polypropylene microporous filtering membrane, process is: polypropylene is film extrusion under higher than its fusing point first, then in tension-free situation, be placed on below polypropylene fusing point to cool, time is no more than 5 s, then film punching is then controlled certain stretch ratio to stretch, then by film thermoforming at certain temperature and tension force, thus obtained required perforated film.The product that stretching method and rays method obtain is soft thin products, has certain difficulty when producing hard or thick article.
Adopt supercutical fluid reduction of blood pressure in high-speed legal system for the foam materials of thermoplastic polymer, what generally obtain is the foam materials with unicellular structure, independent of one another between abscess and abscess.Summer broad sense (summer broad sense, Master's thesis, Dalian University of Technology, Dalian, 2010) adopt the treating processes of the supercritical co step-down foaming gas injection continuous warming repeatedly release improved to prepare polymethylmethacrylate (PMMA) porous material, sample interior abscess has connectedness to a certain degree.But experiment complex disposal process, foam structure is wayward, and the size of sample interior abscess is comparatively large, not in the scope of cellular plastic.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the polymer foams of open-celled structure, described method technique is simple, the product distribution of cells prepared according to the method for the invention evenly and foam material inclusion-free remain.
Have a preparation method for the polymer foams of open-celled structure, processing step is as follows:
(1) adopt scorification to be undertaken blended by two or more polymkeric substance, obtain the blend of polymkeric substance;
(2) the blend vacuum mold of polymkeric substance step (1) obtained is pressed into the base substrate of design shape and cooling and shaping;
(3) the blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into gas and more than the super critical point of the described gas that heats up, is forced into be converted into supercutical fluid, after supercutical fluid reaches capacity state in base substrate, adopt reduction of blood pressure in high-speed method that base substrate is foamed, after cooling and shaping, obtain polymeric foamable material;
(4) immerse in suitable etching liquid by the polymeric foamable material that step (3) obtains, namely certain hour obtains the polymer foams with open-celled structure after taking out;
(5) polymer foams with open-celled structure step (4) obtained is successively with the impurity that ethanol, distilled water repetitive scrubbing have in the polymer foams of open-celled structure with removing.
In aforesaid method, polymkeric substance is thermoplastic polymer, can be unformed thermoplastic polymer, or crystalline thermoplastic polymkeric substance.
In aforesaid method, the operation of scorification is as follows: the blend of polymkeric substance is mixing even to mixed with polymers under the common melt temperature of normal pressure, blend polymer.
In aforesaid method, the gas for foaming is carbonic acid gas, nitrogen or air.
In aforesaid method, the rate of pressure reduction (mean rate) of reduction of blood pressure in high-speed foaming is 5 ~ 60 MPa/s.
In aforesaid method, the etching liquid that polymeric foamable material immerses can be a kind of solution, a kind of solvent or its mixed solution.To the requirement of etching liquid be: etching liquid can produce physics or chemical reaction with polymeric foamable material, make in polymeric foamable material, to have at least a kind of polymkeric substance dissolved or degrade, cell wall is formed the passage connecting abscess, and final formation has the polymer foams of open-celled structure.
In aforesaid method, the polymeric foamable material time be immersed in etching liquid is 30 min ~ 4 h, and etching liquid temperature is 15 ~ 65 DEG C.
The invention has the beneficial effects as follows: first, the polymer foams of prepared by the method for the invention have open-celled structure, abscess is Open architecture, can form complicated passage between abscess, be suitable as sound-absorbing, absorption and special separation material, be also applicable to Thermosensitive Material Used for Controlled Releasing of Medicine; The second, the present invention is the novel method that polymer foams forms that open-celled structure provides a kind of difference design; 3rd, the polymer foams of prepared by the method for the invention have open-celled structure, can by controlling saturation pressure, temperature of saturation, rate of pressure reduction, polymeric foamable material be immersed in the experiment conditions such as time in etching liquid and control its cell morphology, with satisfied different needs; 4th, the conventional gas under the method for the invention employing supercritical state is as whipping agent, with low cost, is conducive to environment protection; 5th, the method for the invention technique is simple, adopts conventional equipment processing, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph with the polymer foams section of open-celled structure prepared by embodiment 1.
Accompanying drawing 2 is the scanning electron microscope (SEM) photographs with the polymer foams section of open-celled structure prepared by embodiment 2.
Embodiment
Below in conjunction with embodiment, technology bill of the present invention is further described, but it is important to point out, embodiment can not be interpreted as limitation of the present invention.
In following embodiment, polymethylmethacrylate (PMMA) is produced by sumitomo chemical company, model LG2; Poly(lactic acid) (PLA) is produced by NatureWorks company, model 2002D; General Purpose Polystyrenre (PS), Ningbo platform, the trade mark is 5250; Polycaprolactone (PCL) is produced by Sigma-Aldrich; Polycarbonate (PC) changes into company by Japanese Supreme Being people and produces, model K-1300.
embodiment 1
(1) be that 80:20 prepares burden by polymethylmethacrylate and polystyrene mass ratio, normal pressure, at 200 DEG C in torque rheometer mixing 8 min, obtain the blend of polymkeric substance;
(2) blend of polymkeric substance step (1) obtained carries out vacuum compression molding, and molding temperature is 200 DEG C, and dwell pressure is 10 MPa, and the dwell time is 7 min, obtains sheet blend base substrate that thickness is the polymkeric substance of 0.8 mm and cooling and shaping;
(3) the sheet blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into carbonic acid gas, pressure-controlling in reactor is at 20 MPa, temperature controls at 90 DEG C, after supercritical co reaches capacity state in base substrate, with the release speed of about 15 MPa/s by the Pressure Drop in reactor to normal pressure, obtain polymeric foamable material after cooling and shaping;
(4) be immersed in the hexanaphthene under room temperature by the polymeric foamable material that step (3) obtains, the immersion time is 2 h, namely obtains the polymer foams with open-celled structure;
(5) polymer foams with open-celled structure step (4) obtained is successively with the impurity that ethanol, distilled water repetitive scrubbing have in the polymeric foamable material of open-celled structure with removing.
The product prepared by the present embodiment with liquid nitrogen carries out brittle failure, scanning electron microscope (SEM) is adopted to observe its section, Fig. 1 is the scanning electron microscope (SEM) photograph with the polymer foams section of open-celled structure prepared by embodiment 1, as can be seen from the figure cell wall there are many apertures, illustrate that this is the polymer foams with open-celled structure.
The percentage of open area utilizing true density instrument to record the present embodiment products obtained therefrom is 68%.
embodiment 2
(1) be that 80:20 prepares burden by polymethylmethacrylate and poly(lactic acid) mass ratio, normal pressure, at 180 DEG C in torque rheometer mixing 8 min, obtain the blend of polymkeric substance;
(2) blend of polymkeric substance step (1) obtained carries out vacuum compression molding, and molding temperature is 180 DEG C, and dwell pressure is 5 MPa, and the dwell time is 5 min, obtains sheet blend base substrate that thickness is the polymkeric substance of 0.8 mm and cooling and shaping;
(3) the sheet blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into carbonic acid gas, pressure-controlling in reactor is at 20 MPa, temperature controls at 90 DEG C, after supercritical co reaches capacity state in base substrate, with the release speed of about 15 MPa/s by the Pressure Drop in reactor to normal pressure, obtain polymeric foamable material after cooling and shaping;
(4) polymeric foamable material that step (3) obtains is immersed in the mixed solution of the phosphate buffered saline buffer (PH=8.2) that volume ratio is 1:1 and ethanol, mixeding liquid temperature is 60 DEG C, the immersion time is 30 min, namely obtains the polymer foams with open-celled structure;
(5) polymer foams with open-celled structure step (4) obtained is successively with the impurity that ethanol, distilled water repetitive scrubbing have in the polymer foams of open-celled structure with removing.
The product prepared by the present embodiment with liquid nitrogen carries out brittle failure, adopts scanning electron microscope (SEM) to observe its section.Fig. 2 is the scanning electron microscope (SEM) photograph with the polymer foams section of open-celled structure prepared by embodiment 2, the as we can see from the figure mutual UNICOM of abscess.
The percentage of open area utilizing true density instrument to record the present embodiment products obtained therefrom is 60%.
embodiment 3
(1) be that 20:80 prepares burden by polymethylmethacrylate and polystyrene mass ratio, normal pressure, at 200 DEG C in torque rheometer mixing 8 min, obtain the blend of polymkeric substance;
(2) identical with embodiment 1 step (2);
(3) the sheet blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into carbonic acid gas, pressure-controlling in reactor is at 20 MPa, temperature controls at 90 DEG C, after supercritical co reaches capacity state in base substrate, with the release speed of about 20 MPa/s by the Pressure Drop in reactor to normal pressure, obtain polymeric foamable material after cooling and shaping;
(4) be immersed in acetic acid by the polymeric foamable material that step (3) obtains, the immersion time is 3 h, namely obtains the polymer foams with open-celled structure;
(5) identical with embodiment 1 step (5).
The percentage of open area utilizing true density instrument to record the present embodiment products obtained therefrom is 63%.
embodiment 4
(1) be that 80:20 prepares burden by polycaprolactone and polystyrene mass ratio, normal pressure, at 180 DEG C in torque rheometer mixing 8 min, obtain the blend of polymkeric substance;
(2) identical with embodiment 2 step (2);
(3) identical with embodiment 1 step (3);
(4) identical with embodiment 1 step (4);
(5) identical with embodiment 1 step (5).
The percentage of open area utilizing true density instrument to record the present embodiment products obtained therefrom is 65%.
embodiment 5
(1) be that 80:20 prepares burden by polycarbonate and polystyrene mass ratio, normal pressure, at 200 DEG C in torque rheometer mixing 8 min, obtain the blend of polymkeric substance;
(2) identical with embodiment 1 step (2);
(3) the sheet blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into carbonic acid gas, pressure-controlling in reactor is at 20 MPa, temperature controls at 180 DEG C, after supercritical co reaches capacity state in base substrate, with the release speed of about 15 MPa/s by the Pressure Drop in reactor to normal pressure, obtain polymeric foamable material after cooling and shaping;
(4) identical with embodiment 1 step (4);
(5) identical with embodiment 1 step (5).
The percentage of open area utilizing true density instrument to record the present embodiment products obtained therefrom is 62%.
Claims (5)
1. there is a preparation method for the polymer foams of open-celled structure, it is characterized in that processing step is as follows:
(1) adopt melt-blending process by polymethylmethacrylate and polystyrene, or polycaprolactone and polystyrene, or polycarbonate and polystyrene carry out blended, obtain the blend of polymkeric substance;
(2) the blend vacuum mold of polymkeric substance step (1) obtained is pressed into the base substrate of design shape and cooling and shaping;
(3) the blend base substrate of polymkeric substance step (2) obtained is placed in autoclave, pass into gas and more than the super critical point of the described gas that heats up, is forced into be converted into supercutical fluid, after supercutical fluid reaches capacity state in base substrate, adopt reduction of blood pressure in high-speed method that base substrate is foamed, after cooling and shaping, obtain polymeric foamable material;
(4) polymeric foamable material step (3) obtained immerses in etching liquid, and namely certain hour obtains the polymer foams with open-celled structure after taking out; Described etching liquid is hexanaphthene or acetic acid.
2. a kind of preparation method with the polymer foams of open-celled structure according to claim 1, is characterized in that described is carbonic acid gas, nitrogen or air for the gas foamed.
3. a kind of preparation method with the polymer foams of open-celled structure according to claim 1, it is characterized in that the described polymeric foamable material time be immersed in etching liquid is 30min ~ 4h, etching liquid temperature is 15 ~ 65 DEG C.
4. a kind of preparation method with the polymer foams of open-celled structure according to claim 1, is characterized in that the operation of described scorification is as follows: the blend of polymkeric substance is mixing even to mixed with polymers under the common melt temperature of normal pressure, blend polymer.
5., according to a kind of preparation method with the polymer foams of open-celled structure one of Claims 1-4 Suo Shu, it is characterized in that the blend base substrate of polymkeric substance adopts the foaming of reduction of blood pressure in high-speed method, the rate of pressure reduction of described reduction of blood pressure in high-speed is 5 ~ 60MPa/s.
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| CN105001512B (en) * | 2015-07-01 | 2017-06-27 | 中国科学院宁波材料技术与工程研究所 | A kind of open cell polymer foams and preparation method thereof |
| CN106806946A (en) * | 2016-12-05 | 2017-06-09 | 四川大学 | Polymer tissue engineering stephanoporate stent material of organic solvent-free residual and preparation method thereof |
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| CN109082049B (en) * | 2018-06-19 | 2021-06-15 | 嘉兴南洋职业技术学院 | Supercritical fluid foaming fluorine-containing polymer material and preparation method thereof |
| CN110480913B (en) * | 2019-09-24 | 2023-08-18 | 四川大学 | Self-balancing supercritical foaming method and device for multi-component multiphase complex system |
| CN113372642A (en) * | 2021-06-30 | 2021-09-10 | 北京冬曦既驾科技咨询有限公司 | Antibacterial toughening type polyethylene film and preparation method thereof |
| CN115926335B (en) * | 2022-12-07 | 2024-04-12 | 四川大学 | Method for constructing non-cortex porous structure on polymer surface by high-pressure gas foaming technology |
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| CN1293129C (en) * | 2004-10-14 | 2007-01-03 | 北京化工大学 | Method for preparing Nano film of multiporous polyimide in low dielectric constant |
| CN101920043B (en) * | 2010-08-17 | 2013-10-16 | 复旦大学 | Porous bracket with micro grooves on pore walls and preparation method thereof |
| CN102796277B (en) * | 2012-08-03 | 2014-04-09 | 四川大学 | Gradient biocompatible polymer foaming material with opening structure and preparation method thereof |
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