CN103128973A - Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure - Google Patents
Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a high polymer product provided with a multi-scale foam structure. The method includes that raw materials are molded to be samples, then the samples are placed in an autoclave, supercritical fluid is introduced into the autoclave, pressure is maintained, or the raw materials and the supercritical fluid are simultaneously added into a molding device, the synergistic effect of temperature rise and pressure relief is utilized to foam high polymer materials, and different foaming performances of the high polymer materials are combined to manufacture the high polymer product provided with the multi-scale foam structure. Compared with a common foaming method, the preparation method of the high polymer product provided with the multi-scale foam structure can improve connectivity of the manufactured product which can be used for aspects such as tissue engineering, super-hydrophobic, filtering and the like. Besides, the method is less in process, capable of achieving batch production, and easy to promote in industrial production.
Description
Technical field
The present invention relates to foaming macromolecular goods preparing technical field, particularly have the high molecular products preparation method of multiple dimensioned foam structure.
Background technology
High molecular products with multiple dimensioned foam structure refers to that there is the new material of the abscess of two or more different size in a kind of section within it.This material has the excellent properties of various different size abscesses, has a lot of potential applications.Than common foaming product, have the surface of high molecular products of multiple dimensioned foam structure and the contact angle of other materials and greatly improve, thereby expand the application of macromolecular material aspect super-hydrophobic; Macromolecular material than the single size foam structure, the mechanical property of macromolecular material with multiple dimensioned foam structure is better, and degree of communication is higher, more is conducive to the inflow that makes Growth of Cells required, the cell excreta is flowed out, thereby be more suitable for for the bioengineered tissue material; The macromolecular material of multiple dimensioned foam structure is playing filter aid as in filter medium.Therefore, the macromolecular material that has a multiple dimensioned foam structure can be applicable to the fields such as organizational project, super-hydrophobic, filtration.
At present, generally adopt autoclave to prepare the macromolecular material of two yardstick foam structures by the method for two step pressure releases with intermittent mode.Yet this method production efficiency is low, not can manufacture, and is unfavorable for promoting in industrial production.In addition, this method has higher requirement to pressure relief system, namely requires equipment to have pressure release to a certain force value and the function of pressure release again after keeping certain hour, and the method can only obtain two yardsticks and can not obtain the macromolecular material of more multiple dimensioned foam structure.Therefore, the preparation method who seeks a kind of more easy, effective, continuous multiple dimensioned foam structure macromolecular material has huge practical significance and theory value.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of simple to operate, work flow is reasonable, equipment requirement is less, process stabilizing is reliable and can be used for industrial high molecular products preparation method with multiple dimensioned foam structure.
Another object of the present invention is to provide a kind of application of high molecular products of above-mentioned multiple dimensioned foam structure.
The first technical scheme that the present invention's preparation has multiple dimensioned foam structure high molecular products comprises the steps:
(1) raw material is added carry out melting in former, be shaped to elementary goods;
(2) elementary goods are put into autoclave;
(3) after supercritical fluid forms and is in supercriticality with induction system control gas, be injected in autoclave, make elementary goods continue saturated 0.5 ~ 24h under the saturation pressure of the saturation temperature of 30 ~ 300 ℃ and 7 ~ 50MPa, autoclave be warming up to than saturation temperature high more than 10 ℃ blowing temperature and keep 0.1 ~ 3h, make at last the autoclave quick pressure releasing, obtain having the high molecular products of multiple dimensioned foam structure.
Described in step (1), former is injection machine or extruder, and extruder is single screw extrusion machine or double screw extruder.
Described in step (1), raw material is the macromolecular material of one-component, is perhaps the macromolecule heterogeneous system, comprises the blend that is made of two or more macromolecular material, and the composite that is made of macromolecular material and inorganic material.Described macromolecular material is Biodegradable material or common high molecular materials.Biodegradable material is specially PLA, polyvinyl alcohol, polycaprolactone, poly butylene succinate, starch, polyethylene glycol oxide, polyglycolic acid or polyhydroxyalkanoate; Common high molecular materials is specially polypropylene, polyethylene, nylon, polymethyl methacrylate or polystyrene.Described inorganic material is specially nanometer particle, comprises mica, imvite, halloysite nanotubes, CNT, silica or calcium carbonate, or micro-size particles, comprises glass fibre or glass microballoon.
Supercritical fluid described in step (3) is supercritical carbon dioxide or overcritical nitrogen.
Have in the high molecular products of multiple dimensioned foam structure described in step (3), the average diameter of one-level abscess (being maximum abscess) is 40 ~ 1000 μ m, the average diameter of secondary abscess is 5% ~ 50% of one-level abscess average diameter, and the average diameter of n level abscess is 5% ~ 50% of (n-1) level abscess average diameter.
The second technical scheme that the present invention's preparation has multiple dimensioned foam structure high molecular products comprises the steps:
(1) raw material is added carry out melting in former, form melt;
(2) after supercritical fluid forms and is in supercriticality with induction system control gas, be injected in melt;
(3) supercritical fluid that injects and melt carry out mixing, after forming single phase soln, and the injection moulding mould, simultaneously quick release pressure makes the flux foaming moulding, obtains having the high molecular products of multiple dimensioned foam structure.
In step (3), mixing flow field comprises and shears flow field, elongation flow field and chaos flow field.
The classification of the kind of macromolecular material and inorganic material, supercritical fluid and former is all identical with the first scheme.
The third technical scheme that the present invention preparation has a multiple dimensioned foam structure high molecular products is that the high molecular products with multiple dimensioned foam structure with the preparation of the second technical scheme is as elementary foaming product, elementary foaming product is placed in heating cabinet or hot stove, elementary expanded material carries out second time of foaming, obtain the second time of foaming material, the second time of foaming material is the high molecular products with more multiple dimensioned foam structure.
By the high molecular products with multiple dimensioned foam structure of above-mentioned three kinds of schemes preparation, can be applicable to the association areas such as organizational project, super-hydrophobic and filtration.
The preparation method of above-mentioned three kinds of schemes is synergies of utilizing pressure release or itself and heating up, and has the high molecular products of multiple dimensioned foam structure in conjunction with the difference preparation of various macromolecular material foam performances.Wherein the principle of the first scheme is as described below.When raw material is the macromolecular material of one-component, after supercritical fluid reaches capacity in material, improve temperature and produce large thermodynamic instability to blowing temperature to produce a large amount of nuclei of bubbles in material, nuclei of bubbles is grown up gradually and is formed larger abscess afterwards; During quick pressure releasing, in macromolecular material not foamed zones can produce a large amount of nuclei of bubbles, finally form minute bubbles; Like this, the synergy by intensification and pressure release makes macromolecular material form the foam structure of two yardsticks under the environment of supercritical fluid.And during the blend that consists of for two or more macromolecular material when raw material, except the principle of the two yardstick foam structures of above-mentioned formation, also have the factor of two aspects can cause abscess to present Multi-scale model.Viscosity, melt strength, the solubility of supercritical fluid in each macromolecular material of each macromolecular material are different with diffusion rate on the one hand, and foamable temperature range is also different, causes each macromolecular material to form the abscess of different size under identical conditions.And, for inconsistent heterogeneous system, the two-phase interface cohesive force a little less than, free energy is less, heat up or pressure leak process in, oversaturated supercritical fluid is hoarded at the two-phase interface place, forms the cavity after solidifying, thereby forms large abscess.The reason of this two aspect causes the macromolecular material heterogeneous system to form multiple dimensioned foam structure.
It is as described below that first scheme preparation has the concrete principle of high molecular products of multiple dimensioned foam structure.After supercritical fluid reached capacity in macromolecular material, quick pressure releasing produced large thermodynamic instability to produce a large amount of nuclei of bubbles in material.Because viscosity, melt strength, solubility and the diffusion rate of supercritical fluid in each macromolecular material of each macromolecular material are different, foamable temperature range is also different, causes each macromolecular material to form the abscess of different size under identical conditions.And, for inconsistent heterogeneous system, the two-phase interface cohesive force a little less than, free energy is less, heat up or pressure leak process in, oversaturated supercritical fluid is hoarded at the two-phase interface place, forms the cavity after solidifying, thereby forms large abscess.The reason of this two aspect causes the macromolecular material heterogeneous system to form multiple dimensioned foam structure.
concrete principle and first scheme difference that the third scheme preparation has the high molecular products of multiple dimensioned foam structure are: still have supersaturated gas in the high molecular products with multiple dimensioned foam structure by the first scheme preparation, when the environment that these goods is placed in higher than the vitrification point of macromolecular material, supersaturated vapor in material is known from experience makes the not foamed zones of material can produce a large amount of nuclei of bubbles, the final minute bubbles that form, thereby material is acted synergistically under the environment of supercritical fluid by pressure release and intensification, obtain having the high molecular products of multiple dimensioned foam structure.
The present invention has following beneficial effect with respect to prior art:
(1) this Polymer materialspreparation method operation is less, and the equipment that adopts is continuous type process equipment (being extruder or injection machine) comparatively general in industrial production, therefore guaranteed the continuity of producing, can realize batch production, be easy to promote in industrial production, have wide prospects for commercial application.
(2) this high molecular products preparation method foams to macromolecular material in conjunction with the synergy of intensification and pressure release, with respect to common foaming method, can improve the degree of communication of high molecular products.
(3) this high molecular products preparation method has the high molecular products of multiple dimensioned foam structure by intensification and the preparation of pressure release synergy.For the macromolecular material of one-component, adopt this method by regulating saturation temperature, saturation pressure, blowing temperature, saturation time etc., can obtain the high molecular products of two yardstick foam structures of different large and small abscess-sizes.For the macromolecule heterogeneous system, foam structure after foaming is except the impact that is subjected to technological parameter, also can be by viscosity, melt strength and supercritical fluid solubility and the diffusion rate in each phase component of each phase component of regulation and control, perhaps form different phase morphologies, can prepare the high molecular products with multiple dimensioned foam structure.
Description of drawings
Fig. 1 is the variation schematic diagram that the present invention has temperature and pressure in multiple dimensioned foam structure high molecular products preparation method implementation process.In figure, solid line represents variations in temperature, and dotted line represents that pressure changes, T
FBe blowing temperature, T
SBe saturation temperature, P
FBe blow pressure.
Fig. 2 is the process schematic diagram when adopting this high molecular products preparation method to prepare single macromolecular material to have multiple dimensioned foam structure.
Fig. 3 is the heterogeneous system that adopts this high molecular products preparation method the to prepare sea-island structure process schematic diagram when having multiple dimensioned foam structure.
Fig. 4 is the heterogeneous system that adopts this high molecular products preparation method the to prepare filamentary structure process schematic diagram when having multiple dimensioned foam structure.
Fig. 5 is the heterogeneous system that adopts this high molecular products preparation method the to prepare common continuous phase structure process schematic diagram when having multiple dimensioned foam structure.
Fig. 6 A is polystyrene electron scanning micrograph after intensification and the foaming of pressure release synergy in autoclave.
Fig. 6 B is the interior partial enlarged drawing of the square frame of Fig. 6 A.
Fig. 7 A is the surface of not expanded polystyrene (EPS) and the wetting state figure of water.
Fig. 7 B is the surface of expanded polystyrene (EPS) and the wetting state figure of water.
Fig. 8 A is PLA electron scanning micrograph after intensification and the foaming of pressure release synergy in autoclave.
Fig. 8 B is the interior partial enlarged drawing of the square frame of Fig. 8 A.
Fig. 9 A is that blowing temperature is 150 ° of C, and when blow pressure was 14MPa, adopting supercritical fluid was electron scanning micrograph after 70/30 polystyrene/polylactic acid blend foaming to the volume ratio by mixing preparation.
Fig. 9 B is the interior partial enlarged drawing of the square frame of Fig. 9 A.
Figure 10 A is that blowing temperature is 140 ° of C, and when blow pressure was 14MPa, adopting supercritical fluid was electron scanning micrograph after 70/30 polystyrene/polylactic acid blend foaming to the volume ratio by mixing preparation.
Figure 10 B is the interior partial enlarged drawing of the square frame of Figure 10 A.
In above-mentioned each figure, each label is as follows respectively: the 1-supercritical fluid; The large abscess of 2-; The 3-small cells; The few component phase of 4-; 5-multicomponent phase; 6-PLA phase; 7-polystyrene phase.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of high molecular products preparation method with two yardstick foam structures of the present embodiment comprises the steps:
(1) with the PS(polystyrene) pellet adds extruder, and extrude the preparation diameter and be about 1mm, longly be the bar-shaped batten of PS of 10mm;
(2) the bar-shaped batten of PS of step (1) preparation is put into autoclave, under the condition of 30 ℃ of saturation temperatures, saturation pressure 14MPa, pass into supercritical CO
2, after continuing saturated 5h, be warming up to the blowing temperature of 100 ℃, after keeping 40min, the pressure in the autoclave chamber is down to atmospheric pressure in 1s, obtain having the PS goods of two yardstick foam structures.
Fig. 6 A and Fig. 6 B are depicted as the electron scanning micrograph of the PS of above-mentioned preparation.As can be seen from the figure, formed the foam structure of two yardsticks in prepared PS goods, the abscess average diameter of large and small abscess is about respectively 50.0 μ m and 10.5 μ m, and cell density is about respectively 2.4 * 10
8Cells/cm
3With 1.5 * 10
9Cells/cm
3The average diameter of small cells is 21% of large abscess.
Be respectively not foam PS and the surface of foam PS goods and the surface contact angle figure of water shown in Fig. 7 A and Fig. 7 B.As can be seen from Figure, the contact angle (87.1 °) that has the obvious PS greater than not foaming of contact angle (153.3 °) of the PS goods of two yardstick foam structures.
Embodiment 2
The present embodiment is a kind of high molecular products preparation method with two yardstick foam structures, comprises the steps:
(1) with the PLA(PLA) pellet adds extruder, and extrude the preparation diameter and be about 1mm, longly be the bar-shaped batten of PLA of 10mm;
(2) the bar-shaped batten of PLA of step (1) preparation is put into autoclave, under the condition of 100 ℃ of saturation temperatures, saturation pressure 14MPa, pass into supercritical CO
2, after continuing saturated 3h, be warming up to the blowing temperature of 150 ℃, after keeping 40min, the pressure in the autoclave chamber is down to atmospheric pressure in 1s, obtain having the PLA goods of two yardstick foam structures.
Fig. 8 A and Fig. 8 B are the electron scanning micrograph of the PS of above-mentioned preparation.As can be seen from the figure, two yardstick foam structures of perforate have been formed after the PLA foaming.
Embodiment 3
A kind of high molecular products preparation method with two yardstick foam structures of the present embodiment comprises the steps:
(1) by volume take 70 parts of PS and 30 parts of PLA, and mix;
(2) mixture with step (1) adds in extruder, extrudes the preparation diameter and is about 1mm, long is the PS/PLA blend of 10mm;
(3) the PS/PLA blend of step (2) preparation is put into autoclave, under the condition of 100 ℃ of saturation temperatures, saturation pressure 14MPa, pass into supercritical CO
2, after continuing saturated 3h, be warming up to the blowing temperature of 150 ℃, after keeping 40min, the pressure in the autoclave chamber is down to atmospheric pressure in 1s, obtain having the foam PS of two yardstick foam structures/PLA blend.
Fig. 9 A and Fig. 9 B are depicted as the electron scanning micrograph of the PS/PLA blend of above-mentioned preparation.As can be seen from the figure, the blend after foaming presents two yardstick foam structures, and by statistics, PLA is about respectively 44.64 μ m and 15.76 μ m with PS abscess average diameter mutually.
The Polymer materialspreparation method of a kind of multiple dimensioned foam structure of the present embodiment comprises the steps:
(1) by volume take 70 parts of PS and 30 parts of PLA particles, and mix;
(2) mixture with step (1) adds in extruder, extrudes the preparation diameter and is about 1mm, long is the PS/PLA blend of 10mm;
(3) the PS/PLA blend of step (2) preparation is put into autoclave, under the condition of 100 ℃ of saturation temperatures, saturation pressure 14MPa, pass into supercritical CO
2, after continuing saturated 3h, be warming up to the blowing temperature of 140 ℃, after keeping 40min, the pressure in the autoclave chamber is down to atmospheric pressure in 1s, obtain having the foam PS of two yardstick foam structures/PLA blend.
Figure 10 A and Figure 10 B are depicted as the electron scanning micrograph of the PS/PLA blend after foaming.As can be seen from the figure, present multiple dimensioned foam structure in the blend after foaming, formed large abscess in PLA phase and two-phase interface place, formed less abscess at PS in mutually.
In above-mentioned each embodiment, preparation method's principle is identical: the synergy of utilizing pressure release or itself and heating up, and in conjunction with the difference of various macromolecular material foam performances, preparation has the high molecular products of multiple dimensioned foam structure, the variation of temperature and pressure (in figure, solid line represents variations in temperature, and dotted line represents that pressure changes) as shown in Figure 1 in preparation process.When raw material is the macromolecular material of one-component, after supercritical fluid reaches capacity in material, improve temperature and produce large thermodynamic instability to blowing temperature to produce a large amount of nuclei of bubbles in material, nuclei of bubbles is grown up gradually and is formed larger abscess afterwards; During quick pressure releasing, in macromolecular material not foamed zones can produce a large amount of nuclei of bubbles, finally form minute bubbles; Like this, the synergy by intensification and pressure release under the environment of supercritical fluid makes macromolecular material form the foam structure of two yardsticks, and the forming process of abscess as shown in Figure 2.And during the blend that consists of for two or more macromolecular material when raw material, except the principle of the two yardstick foam structures of above-mentioned formation, also have the factor of two aspects can cause abscess to present Multi-scale model.Viscosity, melt strength, the solubility of supercritical fluid in each macromolecular material of each macromolecular material are different with diffusion rate on the one hand, foamable temperature range is also different, cause under identical conditions each macromolecular material form different size abscess and, for inconsistent heterogeneous system, the two-phase interface cohesive force a little less than, free energy is less, in intensification or pressure leak process, oversaturated supercritical fluid is hoarded at the two-phase interface place, forms the cavity after solidifying, thereby forms large abscess.The reason of this two aspect causes the macromolecular material heterogeneous system to form multiple dimensioned foam structure.When the phase morphology of blend was sea-island structure, the forming process of blend abscess in foaming process as shown in Figure 3; When the phase morphology of blend was filamentary structure, the forming process of blend abscess in foaming process as shown in Figure 4; When the phase morphology of blend was common continuous phase structure, the forming process of blend abscess in foaming process as shown in Figure 5.
As mentioned above, just can realize preferably the present invention, above-described embodiment is only preferred embodiment of the present invention, is not to limit practical range of the present invention; Be that all equalizations of doing according to content of the present invention change and modify, all contained by claim of the present invention scope required for protection.
Claims (9)
1. have the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: comprise the steps:
(1) raw material is added carry out melting in former, be shaped to elementary goods;
(2) elementary goods are put into autoclave;
(3) after supercritical fluid forms and is in supercriticality with induction system control gas, be injected in autoclave, make elementary goods continue saturated 0.5 ~ 24h under the saturation pressure of the saturation temperature of 30 ~ 300 ℃ and 7 ~ 50MPa, autoclave be warming up to than saturation temperature high more than 10 ℃ blowing temperature and keep 0.1 ~ 3h, make at last the autoclave quick pressure releasing, obtain having the high molecular products of multiple dimensioned foam structure.
2. have according to claim 1 the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: described in step (1), former is injection machine or extruder, and extruder is single screw extrusion machine or double screw extruder.
3. has according to claim 1 the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: the described raw material of step (1) is the macromolecular material of one-component, it is perhaps the macromolecule heterogeneous system, comprise the blend that is consisted of by two or more macromolecular material, and the composite that is consisted of by macromolecular material and inorganic material; Described macromolecular material is Biodegradable material or common high molecular materials.Biodegradable material is specially PLA, polyvinyl alcohol, polycaprolactone, poly butylene succinate, starch, polyethylene glycol oxide, polyglycolic acid or polyhydroxyalkanoate; Common high molecular materials is specially polypropylene, polyethylene, nylon, polymethyl methacrylate or polystyrene; Described inorganic material is specially nanometer particle, comprises mica, imvite, halloysite nanotubes, CNT, silica or calcium carbonate, or micro-size particles, comprises glass fibre or glass microballoon.
4. has according to claim 3 the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: during blend that described raw material consists of for two or more macromolecular material, by viscosity, melt strength and supercritical fluid solubility and the diffusion rate in each phase component that regulates and controls each phase component, perhaps form different phase morphologies, can prepare the high molecular products with multiple dimensioned foam structure; The phase morphology of described blend is sea-island structure, filamentary structure, layer structure or is total to the continuous phase structure.
5. have according to claim 1 the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: described supercritical fluid is supercritical carbon dioxide or overcritical nitrogen.
6. the preparation method who has according to claim 1 the macromolecule system of multiple dimensioned foam structure, it is characterized in that: step (3) is described to be had in the high molecular products of multiple dimensioned foam structure, the average diameter of one-level abscess (being maximum abscess) is 40 ~ 1000 μ m, the average diameter of secondary abscess is 5% ~ 50% of one-level abscess average diameter, and the average diameter of n level abscess is 5% ~ 50% of (n-1) level abscess average diameter.
7. have the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: comprise the steps:
(1) raw material is added carry out melting in former, form melt;
(2) after supercritical fluid forms and is in supercriticality with induction system control gas, be injected in melt;
(3) supercritical fluid that injects and melt carry out mixing, form single phase soln, and inject mould or pump into head, foam by quick release pressure, obtain having the high molecular products of multiple dimensioned foam structure.
8. has according to claim 7 the preparation method of the high molecular products of multiple dimensioned foam structure, it is characterized in that: the high molecular products with multiple dimensioned foam structure that described step (3) obtains is as elementary foaming product, elementary foaming product is placed in heating cabinet or hot stove, make elementary foaming product carry out second time of foaming, obtain having the high molecular products of more multiple dimensioned abscess.
9. the described preparation method with high molecular products of multiple dimensioned foam structure of according to claim 1 ~ 8 any one, it is characterized in that: the prepared PS goods with multiple dimensioned foam structure, the contact angle of its section and water is 153.3 °, can be used as super hydrophobic material.
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