CN114953241B - Mixing device and method for polymer matrix nanocomposite by gas cooperative rolling - Google Patents
Mixing device and method for polymer matrix nanocomposite by gas cooperative rolling Download PDFInfo
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- CN114953241B CN114953241B CN202210576898.1A CN202210576898A CN114953241B CN 114953241 B CN114953241 B CN 114953241B CN 202210576898 A CN202210576898 A CN 202210576898A CN 114953241 B CN114953241 B CN 114953241B
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- 238000002156 mixing Methods 0.000 title claims abstract description 66
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000011159 matrix material Substances 0.000 title claims abstract description 26
- 238000005096 rolling process Methods 0.000 title claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 62
- 238000003860 storage Methods 0.000 claims description 29
- 239000013339 polymer-based nanocomposite Substances 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000002195 synergetic effect Effects 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 50
- 230000008569 process Effects 0.000 abstract description 27
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000737 periodic effect Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
- B29B7/56—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
Abstract
The application provides a mixing device and a mixing method for a polymer matrix nanocomposite by gas collaborative rolling, wherein the device comprises the following steps: a frame; a first roller; a second roller; at least one pneumatic valve located within the second roller; a gas cylinder. According to the application, the first roller can realize the periodic change of the roller gap between the two rollers from large to small to large in the mixing process, the material reflux area between the rollers is continuously destroyed, and the volume of the material is periodically expanded, compressed and expanded under the periodic volume stretching effect, so that the continuous mixing process of the material between the two rollers is strengthened; gas is introduced in the mixing process to realize the function of stretching and dispersing in situ bubbles, and the dispersion and distribution of filling particles are strengthened by the action of stretching bubbles. Meanwhile, the size of the roller gap is periodically changed in the volume stretching and mixing process, so that generated bubbles are compressed when the roller gap is reduced, and the problem that the materials need to be processed for the second time to eliminate the bubbles is avoided.
Description
Technical Field
The application relates to the technical field of polymer material processing, in particular to a mixing device and a mixing method for a polymer matrix nanocomposite by gas collaborative rolling.
Background
Polymers, also known as macromolecular compounds, are those compounds having a relative molecular weight of over ten thousand, which are formed by the predominantly covalent bonding of a plurality of atoms or groups of atoms. The linear or bulk structure of the polymer determines that the polymer has good high elasticity, plasticity, mechanical strength and hardness, and is widely applied to the industrial and daily product production fields. With the development of technology, single polymer materials have difficulty in meeting the performance requirements of diversified applications, and polymer-based composite materials, particularly polymer-based nanocomposite materials, are becoming important and hot points of research in the field of high polymer materials. The nano filler is added into the polymer matrix, so that the crystallization performance, mechanical performance, thermal performance and electrical performance of the polymer matrix composite material are obviously improved, and good processing and forming performance can be maintained. In the preparation of polymer-based nanocomposites, the dispersibility of the nanofiller in the polymer matrix directly determines the properties of the final composite. The nano filler has extremely strong agglomeration force, and agglomerates are extremely easy to form in a polymer matrix, so that the advantages of nano particles are lost, and the polymer cannot be subjected to good performance improvement. Therefore, how to improve the dispersibility of nanoparticles in polymer matrices is a key issue for the preparation and application of polymer-based nanocomposites.
The melt blending method has simple and convenient operation and high efficiency, and is one of the most important methods for preparing the polymer-based nanocomposite. The common processing equipment for the melt blending method comprises a double screw extruder, an internal mixer, an open mill and the like, and the shearing field and the stretching field generated by the processing equipment are utilized to realize the distributed mixing and the dispersed mixing among the multiphase systems of the polymer-based nanocomposite. However, since the conventional screw extruder, internal mixer and open mill are mainly based on the processing principle of shear field dominance, the dispersion capability of the fine particles is insufficient. Based on the processing principle of stretching field dominance, the stronger dispersing and mixing capability between multiple components compared with shearing field is proved to be one of the effective methods for preparing polymer-based nanocomposite materials. For example, the prior art also discloses a novel mixing and dispersing device, which comprises at least one cylinder body and a rotor concentrically arranged in the cylinder body, wherein at least two material passing grooves are formed in the rotor, the space formed by the bottom surface of the material passing grooves and the inner wall of the cylinder is gradually reduced from a feeding end to a discharging end, and when materials flow from the feeding area to the discharging area, the flow area in the material passing grooves is gradually reduced, so that the main flow direction is consistent with the main speed gradient direction when the materials flow, the flow of the materials mainly takes the stretching flow as the main, and the mixing and dispersing device has the advantage of good dispersing performance.
The mill is an important device for preparing polymer-based composites, and the traditional mill is based on the principle of shear-field dominated polymer processing. The open mill is improved and optimized in structure, so that the stretching field dominance can be realized, and the mixing effect in the open mill process is improved. For example, the prior art discloses a method and a device for reinforcing and mixing a polymer material by using an eccentric roller, wherein when a rear roller eccentric to a rotation axis and a front roller concentric to the rotation axis are rotated in opposite directions, a roller gap between the two rollers is periodically changed in size, and a material backflow area between the rollers is continuously damaged, so that a continuous mixing process of materials between the two rollers is reinforced. However, in the process of mixing the polymer and the nano material by using the method, the dispersion effect of the material is not ideal.
Disclosure of Invention
In view of the above, the present application provides a mixing device and a method for rolling polymer-based nanocomposite with gas co-operation, so as to solve or at least partially solve the technical problems existing in the prior art.
In a first aspect, the present application provides a gas co-roll polymer matrix nanocomposite mixing apparatus comprising:
a frame;
the first roller is rotatably arranged on the frame and is an eccentric roller;
the second roller is rotatably arranged on the frame and is parallel to the first roller;
the pneumatic valve is positioned in the second roller, and an air outlet of the pneumatic valve penetrates out of the second roller;
the gas storage bottle is positioned outside the second roller, and the gas outlet of the gas storage bottle is communicated with the pneumatic valve.
Preferably, the gas outlet of the gas storage bottle is communicated with the pneumatic valve through a metal pipeline.
Preferably, the gas cooperated with the roll-in polymer matrix nanocomposite mixing device is characterized in that a pressure regulating valve and a pressure gauge are arranged on the gas outlet of the gas storage bottle.
In a second aspect, the application also provides a gas-assisted roll-in polymer mixing method, which comprises the following steps:
providing the gas collaborative rolling polymer matrix nanocomposite mixing device;
adding polymer and nano material between the first roller and the second roller, and setting the pressure of the gas storage cylinder;
the first roller and the second roller are driven to rotate in opposite directions, the air outlet of the pneumatic valve is opened under the set pressure, inert gas in the gas storage bottle is sprayed out through the air outlet of the pneumatic valve, and the polymer and the nano material are mixed under the rotation of the first roller and the second roller and the action of the inert gas.
The mixing device for the gas-synergetic rolling polymer-based nanocomposite has the following beneficial effects compared with the prior art:
according to the gas collaborative rolling polymer-based nanocomposite mixing device, the rotation axis of the first roller is eccentric with the central line (namely the axis) of the outer circle of the roller, the eccentricity is adjustable, the periodic change of the roller gap between the two rollers from large to small to large in the mixing process is realized, the material reflux area between the rollers is continuously destroyed, the volume of the material is periodically expanded, compressed and expanded under the periodic volume stretching effect, and the continuous mixing process of the material between the two rollers is strengthened; in order to introduce gas (such as nitrogen, which does not react with materials) in the mixing process and realize the function of stretching and dispersing in-situ bubbles, a plurality of pneumatic valves are arranged in the second roller, and air outlets of the pneumatic valves penetrate out of the second roller. When the air pressure is regulated to reach a certain value, the second roller inner pneumatic valve is opened, high-pressure air is discharged, and the high-pressure air is subjected to the action of the wrapping roller of the plasticized material, forms bubbles in the plasticized melt and rapidly expands, and rapidly stretches the surrounding polymer melt, so that the dispersion distribution of filling particles is enhanced by the bubble stretching action. Meanwhile, the size of the roller gap is periodically changed in the volume stretching mixing process, so that generated bubbles are compressed and defoamed in time under the compression action when the roller gap is reduced, and the problem that the mixing materials need to be processed for the second time to eliminate the bubbles is avoided.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a schematic diagram of a mixing device for gas-co-roll-in polymer-based nanocomposite in one embodiment of the application;
FIG. 2 is a schematic diagram of the mechanism of action of the volumetric stretching and mixing of the patent with application number 201810337425. X;
FIG. 3 is a schematic diagram showing the action of the process of stretching and dispersing bubbles in the kneading apparatus of the present application;
FIG. 4 is an SEM image of a molded material of example 1 according to the present application;
FIG. 5 is a TEM image of the molded material of example 1 of the present application;
FIG. 6 is an SEM image of the molded material of comparative example 1;
FIG. 7 is a TEM image of the molded material of comparative example 1;
FIG. 8 is an SEM image of the molded material of comparative example 2;
fig. 9 is a TEM image of the molded material of comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, embodiments of the application. The components of the embodiments of the present application generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the application, as presented in the figures, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present application, it should be understood that, for the convenience of description and simplification of the description, it is not necessary to indicate or imply that the apparatus or elements referred to have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the application, it is that the relation of orientation or position indicated as "upper" is based on the orientation or position relation shown in the drawings, or the orientation or position relation that is conventionally put when the inventive product is used, or the orientation or position relation that is conventionally understood by those skilled in the art.
Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
The following description of the embodiments of the present application will be made in detail and with reference to the embodiments of the present application, but it should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
The embodiment of the application provides a mixing device for a gas collaborative rolling polymer matrix nanocomposite, which is shown in figure 1 and comprises the following components:
a frame 1;
the first roller 2 is rotatably arranged on the frame 1, and the first roller 2 is an eccentric roller;
the second roller 3 is rotatably arranged on the frame 1, and the second roller 3 is arranged in parallel with the first roller 2;
at least one pneumatic valve 4, which is positioned in the second roller 3, wherein the air outlet of the pneumatic valve 4 penetrates out of the second roller 3;
and the gas storage bottle 5 is positioned outside the second roller 3, and the gas outlet of the gas storage bottle 5 is communicated with the pneumatic valve 4.
It should be noted that the mixing device for the gas collaborative rolling polymer matrix nanocomposite in the embodiment of the application comprises a frame 1, a first roller 2 and a second roller 3, wherein the first roller 2 and the second roller 3 are oppositely arranged in parallel, and the first roller 2 and the second roller 3 are both rotatably arranged on the frame 1; the present application does not improve the specific structure of the first roller 2, and the structure of the first roller 2 is completely the same as the structure of the rear roller in the method and the device (application number is 201810337425. X) for reinforcing and mixing the high polymer material by using the eccentric roller in the prior patent. The second roller 3 rotates around the axis of the second roller 3, at least one pneumatic valve 4 is arranged in the second roller 3, the air outlet of the pneumatic valve 4 penetrates out of the second roller 3, and specifically, the air outlet of the pneumatic valve 4 penetrates out of the second roller 3 and is close to the outer peripheral surface of the second roller 3; meanwhile, a gas storage bottle 5 is arranged outside the second roller 3, the gas outlet of the gas storage bottle 5 is communicated with the pneumatic valve 4, and obviously, the gas storage bottle 5 is arranged so that the gas storage bottle can rotate together with the second roller 3; the gas cylinder 5 stores inert gas (which does not react with polymer and nano material), such as nitrogen; the pneumatic valve 4 is adjusted to be opened or closed by adjusting the pressure of the air outlet of the air storage bottle 5, when the pressure of the air outlet of the air storage bottle 5 is adjusted to reach a certain value, the pneumatic valve 4 in the second roller 3 is opened, high-pressure air is discharged from the air outlet of the pneumatic valve 4, and under the action of the wrapping roller of plasticizing materials, the high-pressure air forms bubbles in plasticizing melt and rapidly expands, and the rapid stretching action on surrounding polymer melt is enhanced by the bubble stretching action, so that the dispersion and the distribution of filling particles are enhanced. Meanwhile, the size of the roller gap is periodically changed in the volume stretching mixing process, so that generated bubbles are compressed and defoamed in time under the compression action when the roller gap is reduced, and the problem that the mixing materials need to be processed for the second time to eliminate the bubbles is avoided.
In some embodiments, the gas outlet of the gas cylinder 5 communicates with the pneumatic valve 4 via a metal conduit 6. Namely, one end of the metal pipeline 6 passes through the second roller 3 and is communicated with the pneumatic valve 4 in the second roller 3, and the other end of the metal pipeline is communicated with the air outlet of the air storage bottle 5, and obviously, the second roller 3 drives the air storage bottle 5 to rotate together when rotating.
In some embodiments, a pressure regulating valve 51 and a pressure gauge 52 are provided on the air outlet of the air cylinder 5. The outlet pressure of the gas cylinder 5 can be regulated by providing a pressure regulating valve 51, while the pressure gauge 52 can display a specific pressure value.
According to the mixing device, the rotating axis of the first roller is eccentric with the central line (namely the axis) of the outer circle of the roller, the eccentric distance is adjustable, the periodic change of the roller gap between the two rollers from big to small to big in the mixing process is realized, the material reflux area between the rollers is continuously destroyed, the volume of the material is periodically expanded, compressed and expanded under the periodic volume stretching effect, and the continuous mixing process of the material between the two rollers is strengthened; in order to introduce gas (such as nitrogen, which does not react with materials) in the mixing process and realize the function of stretching and dispersing in-situ bubbles, a plurality of pneumatic valves are arranged in the second roller, and air outlets of the pneumatic valves penetrate out of the second roller. When the air pressure is regulated to reach a certain value, the second roller inner pneumatic valve is opened, high-pressure air is discharged, and the high-pressure air is subjected to the action of the wrapping roller of the plasticized material, forms bubbles in the plasticized melt and rapidly expands, and rapidly stretches the surrounding polymer melt, so that the dispersion distribution of filling particles is enhanced by the bubble stretching action. Meanwhile, the size of the roller gap is periodically changed in the volume stretching mixing process, so that generated bubbles are compressed and defoamed in time under the compression action when the roller gap is reduced, and the problem that the mixing materials need to be processed for the second time to eliminate the bubbles is avoided.
Specifically, fig. 2 shows a schematic diagram of the action mechanism of the volume stretching and kneading of the patent with application number 201810337425. X. FIG. 3 is a schematic view showing the principle of the kneading apparatus of the present application. In FIGS. 2-3, θ is 0, pi/2, pi, 3 pi/2, and 2 pi, which represent that the two rollers are rotated pi/2, pi, 3 pi/2 in opposite directions from the initial position, respectively, and finally return to the initial position.
In fig. 2, the volumetric stretching mixing process is shown (the section line circle represents the section of a rotary shaft of a roller, the excircle represents the surface of the roller), the rotation axis of the roller is eccentric with the center line of the excircle of the roller after design, and the eccentricity e is adjustable, so that the periodic change of the roller gap between the two rollers in the mixing process from small to large is realized, the material backflow area between the rollers is continuously destroyed, and the continuous mixing process of the material between the two rollers is strengthened. In fig. 2, a is an initial position, when the two rollers rotate to the B state, the gap between the two rollers becomes larger, when the two rollers rotate to the C state, the gap between the two rollers becomes largest, when the two rollers rotate to the D state, the gap between the two rollers decreases, and when the two rollers rotate to the E state, the gap between the two rollers becomes smallest.
FIG. 3 is a schematic diagram showing the action of the bubble stretching and dispersing process of the mixing device, after a material plasticizes a wrapping roller (namely a second roller), a pressure regulating valve of a gas storage bottle is regulated to enable the outlet pressure of the gas storage bottle to be an appropriate value, and high-pressure gas is discharged from a gas outlet of the gas storage bottle, under the action of the wrapping roller of the plasticization material, the high-pressure gas forms bubbles in a plasticization melt and rapidly expands (from formation to growth), the rapid stretching action on the surrounding polymer melt strengthens the dispersion and distribution of filling nano particles (black solid circles b in FIG. 3) in a matrix, when a roller gap between two rollers becomes smaller, bubbles formed in the plasticization melt are compressed and defoamed in time, and in the mixing process, the bubbles are continuously formed and defoamed along with the periodical size change of a gap between the two rollers, and the in-situ bubble stretching and dispersing process further strengthens the diffusion and interaction among a polymer multicomponent system. In fig. 3, a is a bubble and b is a nanoparticle; a in fig. 3 is an initial position, where bubbles form nanoparticle agglomeration; in the B state, the gap between the two rollers is enlarged, the bubbles are enlarged, and the nano particles are dispersed; in the state C, the gap between the two rollers reaches the maximum, and the bubbles continue to enlarge the nano particles and continue to disperse; in the D state, the gap between the two rollers is reduced, and at the moment, the bubbles are compressed and deformed, so that the nano particles are well dispersed; in the E state, the gap between the two rollers is the smallest, at which time the bubbles are eliminated by extrusion, and the dispersed nanoparticles enter the polymer melt.
Based on the same inventive concept, the embodiment of the application also provides a gas collaborative rolling polymer mixing method, which comprises the following steps:
s1, providing the gas collaborative rolling polymer matrix nanocomposite mixing device;
s2, adding a polymer and a nano material between the first roller and the second roller, and setting the pressure of the gas storage cylinder;
s3, driving the first roller and the second roller to rotate in opposite directions, opening an air outlet of the pneumatic valve under a set pressure, spraying inert gas in the air storage bottle through the air outlet of the pneumatic valve, and mixing the polymer and the nano material under the rotation of the first roller and the second roller and the action of the inert gas.
The gas-collaborative rolling polymer kneading method of the present application is further described in the following specific examples.
Example 1
The embodiment of the application provides a mixing method of a gas synergetic rolling polymer, which comprises the following steps:
s1, mixing polypropylene and nano titanium dioxide to obtain a mixture, wherein the mass fraction of the nano titanium dioxide in the mixture is 3%;
s2, providing the gas synergetic rolling polymer matrix nanocomposite mixing device, wherein high-pressure nitrogen is stored in the gas storage bottle;
s3, adding the mixture between the first roller and the second roller, controlling the surface temperature of the first roller and the second roller to be 185 ℃, setting the eccentric distance e of the first roller to be 3mm, adjusting the pressure of the air outlet of the air storage bottle to be 8MPa, driving the first roller and the second roller to rotate in opposite directions, opening the pneumatic valve under the action of the air outlet pressure of the air storage bottle, discharging nitrogen from the air outlet of the pneumatic valve, and mixing the mixture for 15min under the action of the opposite rotation of the first roller and the second roller and the nitrogen;
and S4, carrying out compression molding on the mixed mixture by using a flat vulcanizing machine, wherein the compression molding temperature is 185 ℃, and the compression molding time is 8 minutes.
Comparative example 1
This comparative example provides a method of compounding a gas-co-roll polymer, as in example 1, except that the eccentricity e of the first roll is set to 0mm (equivalent to a conventional roll mill), and the remaining steps are the same as in example 1.
Comparative example 2
This comparative example provides a gas-co-roll polymer compounding process, similar to example 1, except that the gas cylinder is closed, no high pressure nitrogen is supplied, and the remainder of the procedure is the same as in example 1.
Performance testing
An SEM image of the molded material of example 1 is shown in fig. 4. A TEM image of the molded material of example 1 is shown in fig. 5. As can be seen from the SEM image of fig. 4, the nano titanium dioxide exists in the matrix polypropylene as single particles or very small agglomerates, and the dispersibility is excellent, and the TEM image of fig. 5 further shows that the nano titanium dioxide exists in the matrix polypropylene mainly as single particles, no obvious agglomeration phenomenon occurs, and the polypropylene/nano titanium dioxide composite material prepared by the gas collaborative rolling polymer mixing method can realize the dispersion and distribution of the nano titanium dioxide in the matrix mainly in the nano particle state, and is beneficial to the strong mixing effect based on the tensile force field formed by the cooperation of the eccentric rolling process and the bubble stretching process.
An SEM image of the molded material of comparative example 1 is shown in fig. 6. A TEM image of the molded material of comparative example 1 is shown in fig. 7. From the SEM image of fig. 6 and the TEM image of fig. 7, it can be observed that the nano titania exists in the matrix polypropylene with obvious agglomerates except a small amount of the nano titania exists as single particles, which indicates that the nano titania cannot be sufficiently and effectively dispersed in the matrix by merely introducing high pressure gas into the polymer melt to generate the action of bubble stretching in the conventional open mill mixing process.
An SEM image of the molded material of comparative example 2 is shown in fig. 8. A TEM image of the molded material of comparative example 1 is shown in fig. 9. From the SEM images of fig. 8 and the TEM images of fig. 9, it can be observed that nano-titania forms more distinct agglomerates in the matrix polypropylene, which show that it is difficult to efficiently open the nanoparticle agglomerates sufficiently by the off-center rolling alone, resulting in dispersion of the nanoparticle-forming agglomerates in the matrix polypropylene.
The mechanical properties of the molded materials of example 1 and comparative examples 1 to 2 were measured as shown in Table 1 below.
TABLE 1 mechanical Properties of the molded materials in example 1 and comparative examples 1 to 2
As can be seen from Table 1, the mechanical properties of the materials prepared in example 1 are much higher than those of the materials prepared in comparative examples 1 to 2. Compared with comparative examples 1 and 2, in example 1, the nano titanium dioxide is well dispersed in the matrix in the state of nano particles after the mixing process of the gas synergistic rolling polymer, and the well dispersed nano particles can better and effectively transfer and dissipate external force, so that the mechanical property is better.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (4)
1. A gas-co-roll polymer-based nanocomposite compounding device, comprising:
a frame;
the first roller is rotatably arranged on the frame and is an eccentric roller;
the second roller is rotatably arranged on the frame and is parallel to the first roller;
the pneumatic valve is positioned in the second roller, and an air outlet of the pneumatic valve penetrates out of the second roller;
the gas storage bottle is positioned outside the second roller, and the gas outlet of the gas storage bottle is communicated with the pneumatic valve.
2. The gas collaborative rolling polymer matrix nanocomposite mixing device of claim 1 wherein the gas outlet of the gas cylinder is in communication with the pneumatic valve through a metal conduit.
3. The gas collaborative rolling polymer matrix nanocomposite mixing device according to claim 2, wherein a pressure regulating valve and a pressure gauge are arranged on the gas outlet of the gas storage cylinder.
4. The gas synergistic rolling polymer mixing method is characterized by comprising the following steps of:
providing a gas co-roll polymer matrix nanocomposite mixing device according to any one of claims 1 to 3;
adding polymer and nano material between the first roller and the second roller, and setting the pressure of the gas storage cylinder;
the first roller and the second roller are driven to rotate in opposite directions, the air outlet of the pneumatic valve is opened under the set pressure, inert gas in the gas storage bottle is sprayed out through the air outlet of the pneumatic valve, and the polymer and the nano material are mixed under the rotation of the first roller and the second roller and the action of the inert gas.
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