CN110480913B - Self-balancing supercritical foaming method and device for multi-component multiphase complex system - Google Patents
Self-balancing supercritical foaming method and device for multi-component multiphase complex system Download PDFInfo
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- CN110480913B CN110480913B CN201910903666.0A CN201910903666A CN110480913B CN 110480913 B CN110480913 B CN 110480913B CN 201910903666 A CN201910903666 A CN 201910903666A CN 110480913 B CN110480913 B CN 110480913B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a foaming and forming process and a device for a non-viscous flow state polymer matrix by mixing and swelling supercritical fluid and a foaming auxiliary agent. In the field of supercritical foaming, the auxiliary foaming agent can promote the diffusion of supercritical fluid in a non-viscous fluid polymer matrix, reduce the foaming temperature of the non-viscous fluid polymer matrix and increase the foaming multiplying power of a foaming product. However, the multi-component multiphase complex system of supercritical fluid, co-blowing agent and non-viscous fluid polymer at high temperature and pressure results in very unstable blowing process of the mixed blowing agent and very unstable cell structure of the foamed article. In order to fully exert the synergistic effect of the auxiliary foaming agent and the supercritical fluid in the aspect of promoting supercritical foaming, the invention provides a process and a device for self-regulating foaming and forming of the supercritical mixed fluid containing the auxiliary foaming agent under a multi-component multiphase system, the self-balancing purpose of the multi-component multiphase complex system under the supercritical foaming condition is realized, the foaming process is finally stabilized, the cell structure is improved, and the product performance is improved.
Description
Technical Field
The invention relates to a method and a device for pressure release foaming after self-balancing swelling in a supercritical state of a multiphase multicomponent complex system, and belongs to the technical field of supercritical foaming.
Background
In recent years, the supercritical foaming method for preparing the microporous polymer foaming material is widely focused on new polymer materials and related industries, and the foaming material prepared by the process has the advantages of large cell density, small pore diameter, excellent performance and the like, and the polymer material suitable for the method is wide in range and environment-friendly in processing process. Although various polymer materials can obtain a porous structure through a supercritical foaming method, for polymer materials with high foaming temperature and low multiplying power, a better foaming effect can be achieved by matching a foaming aid in a supercritical foaming process. However, when the multi-component foaming agent mixed by the supercritical fluid and the auxiliary foaming agent swells the non-viscous polymer, the swelling process is extremely unstable due to the multi-component multiphase complex system, and the fluctuation of the component content or the change of the phase state is extremely easy to occur due to the tiny fluctuation of the temperature or the pressure of the foaming device under the actual running condition, so that the cell structure of the final foaming material is extremely poor, and the corresponding foaming material has poor performance. In order to fully exert the synergistic effect of the supercritical fluid and the auxiliary foaming to remarkably improve the cell structure and macroscopic performance of the foaming material, the stability problem of the multi-component multiphase complex system is needed to be solved.
Patent CN202129925U proposes a set of extrusion foaming device of supercritical carbon dioxide mixed foaming agent, carbon dioxide is fed into an extruder in a liquid state in a constant temperature and constant pressure manner, and metered multicomponent synergetic auxiliary agent accurately together, so that a foamed sheet is continuously and stably produced. However, the process method matched with the device belongs to a foaming method of a viscous polymer matrix, the content of a polymer dissolved foaming agent is related to the content of foaming agent injected, when the content of the foaming agent exceeds the content of the viscous polymer which can be dissolved, the polymer coming out of a die has obvious large cells and obvious defects, so that the polymer is difficult to absorb the maximum content of the foaming agent, and the optimal performance of the foaming material cannot be ensured.
Patent CN108638422a discloses a microcellular injection foaming method using a mixed foaming agent. And (3) uniformly mixing the chemical foaming agent and the polymer granules, adding the mixture into an injection molding machine for plasticizing, and simultaneously injecting the supercritical fluid physical foaming agent for injection foaming molding. The method is foaming of viscous polymer matrix, and the content of polymer dissolved foaming agent is related to the content of foaming agent injection, and the state of saturation and swelling is not reached.
There is also a description of co-blowing agents in an autoclave for foaming in combination with supercritical fluids. The autoclave used in the article has very small cavity<500 ml), the polymer sample size used is also very small [ (]<100 cm 3 ) Therefore, a small-sized polymer sample in a small autoclaveThe multi-component multiphase environment is stable; however, those skilled in the art know: when the equipment is enlarged, because of the complexity of the processes of mixing, reacting, phase changing and the like of materials, an 'enlarging effect' often exists, and the preparation process is different from that of small equipment, so that the performance of the prepared product is obviously different. For the foaming technical field, the auxiliary foaming agent and the supercritical fluid have various phase separation behaviors under different swelling conditions, so that the foaming behavior of the polymer material is unstable under the action of the mixed foaming agent, and particularly, the homogeneous state cannot be effectively maintained under the condition of high content of the auxiliary foaming agent, so that the polymer foaming material with stable cell structure cannot be produced; for laboratory devices, the mixing process is relatively easy due to the small equipment, and the differences in the permeation rates of the blowing agent and the co-blowing agent have limited impact on the production of small equipment, possibly without significant differences; however, once large-scale equipment is used, such differences are significant, often resulting in commercial production results on large-scale equipment that are difficult to achieve as similar to the results of pilot scale. The object of the present invention is to ensure stable preparation of microcellular foamed polymeric materials by means of self-balancing systems in complex states containing two-phase and more multicomponent blowing agents.
In the cavity of the high-pressure container, the supercritical fluid and the auxiliary foaming agent are mutually dissolved to form a homogeneous system and simultaneously swell the polymer material in a non-viscous state. The selected auxiliary foaming agent can be the auxiliary foaming agent suitable for the required foaming polymer material, enhances the swelling effect on a polymer matrix, is suitable for being used as the auxiliary foaming agent of PP, PE and the like due to the factors of molecular structures, and can be used as the auxiliary foaming agent of the polymer matrix due to the reasons of molecular polarity of water, ethanol and the like, can generate strong interaction with PPSU and the like between molecules, and is more suitable for being used as the auxiliary foaming agent of the auxiliary foaming agent.
In the prior art, due to the structure of the auxiliary foaming agent and the polarity of molecules, although CO 2 、N 2 The isosupercritical fluid is the main foaming agent, but the auxiliary foaming agent is more soluble in the polymer material in the swelling process, and the polymer component, the supercritical fluid component and the auxiliary foaming agent are carried out along with the swellingThe agent component reaches an equilibrium state in the polymer rich phase. After the polymer enrichment phase reaches the swelling balance, the inside of the foaming device must ensure the stability of the components of the supercritical enrichment phase. However, the homogeneous state of the polymer-rich phase is very susceptible to phase separation behavior as the supercritical-rich phase component changes. At this time, a region with a large content of supercritical fluid (main foaming agent) and a small content of auxiliary foaming agent will appear in the polymer matrix, resulting in small pore size and large pore density of the cells; at the same time, areas with more co-blowing agent content and less supercritical fluid (main blowing agent) content will also appear, resulting in large cell pore size and small cell density. Finally, the foam hole appearance of the prepared foam material is very unstable and accompanies the phenomenon of big and small holes, and the distribution of the big and small holes and the non-uniformity thereof seriously affect the service performance of a polymer product. Thus, there is a need for new supercritical foaming processes and new apparatus for multi-component multiphase complex systems with self-regulating functions in order to stably produce high performance microcellular foamed polymers.
Disclosure of Invention
The purpose of the invention is that: the problems that in the process of adopting the main foaming agent and the auxiliary foaming agent, the foaming effect of the material fluctuates along with time and the foaming effect is unstable due to the difference of the permeability, the dosage and the like of the main foaming agent and the auxiliary foaming agent in the foaming process are solved. The invention provides a novel supercritical foaming method and a novel device with self-regulating function of a multiphase multi-component complex system, wherein the phase equilibrium state of a main foaming agent and an auxiliary foaming agent can be spontaneously regulated to a stable state at a given temperature and pressure, so that the components of a mixed foaming agent in the swelling process are kept constant, and the uniformity of the pore structure and the performance stability of the finally obtained foaming material are obviously improved.
In a first aspect of the invention, there is provided:
a supercritical foaming method comprising the steps of:
step 1, putting a polymer raw material into a foaming device;
step 2, injecting excessive liquid auxiliary foaming agent into the foaming device, and simultaneously ensuring that the liquid auxiliary foaming agent is not directly contacted with the polymer raw material when in a liquid phase state;
step 3, supplying a main supercritical fluid foaming agent into the foaming device through a constant pressure output system to enable the foaming device to be at a set temperature and pressure;
And step 4, swelling the supercritical fluid and the auxiliary foaming agent by the polymer raw material under the set pressure and temperature conditions, and releasing pressure to foam after reaching a homogeneous saturated state to prepare the porous foaming material.
In one embodiment, after the foaming in the step 4 is completed, the gas in the foaming device is discharged, and after cooling, the auxiliary foaming agent is condensed into a liquid state, and gas-liquid separation is performed, so that the liquid auxiliary foaming agent and the supercritical fluid main foaming agent are recovered.
In one embodiment, the constant pressure gas output means is a booster pump, a buffer tank, and a pressure reducing valve connected in sequence, or an ISCO pump and a buffer tank connected in sequence.
In one embodiment, in step 1, a polymer feedstock is placed in a foaming device through a support member. In step 1, a space for the auxiliary blowing agent enrichment phase is reserved in the foaming device, and the polymer material is placed above the space and is not in contact with the auxiliary blowing agent enrichment phase.
In one embodiment, the co-blowing agent level in step 2 must be excessive but not in contact with the polymer feed. In the step 4, three phases are respectively a polymer enrichment phase dissolved with a supercritical fluid and a co-foaming agent, a supercritical fluid enrichment phase dissolved with a co-foaming agent and a co-foaming agent enrichment phase dissolved with a supercritical fluid in the foaming device.
In one embodiment, in step 3, a temperature increasing treatment is required before the supercritical gas main foaming agent is fed into the foaming device.
In one embodiment, after the foaming device is at the set temperature and pressure in the step 4, the supercritical fluid and the auxiliary foaming agent in the foaming device are in a two-phase equilibrium state with stable components, so that the multi-component complex system (polymer, supercritical fluid and auxiliary foaming agent) in the non-viscous fluid polymer is in a stable homogeneous equilibrium state in the swelling process of physical diffusion. Wherein the space around the polymer material in the foaming device is a supercritical fluid enriched phase with stable components, and the proportion of the supercritical fluid in the phase to the auxiliary foaming agent is only related to the temperature and the pressure of the foaming device. In the swelling process of physical diffusion of the non-viscous polymer in the step 4, although the diffusion rate and the solubility of the supercritical fluid and the auxiliary foaming agent in the polymer matrix are different, the temperature and the pressure of the foaming device are constant, and the proportion of the supercritical fluid and the auxiliary foaming agent in the supercritical fluid enrichment phase is unchanged. Thus, after swelling to saturation, the polymer matrix is in a homogeneous equilibrium state of the multicomponent complex system, the content of the swollen supercritical fluid and the co-blowing agent being dependent only on the temperature and pressure of the foaming device. Thanks to the self-regulating function of the invention, the homogeneous equilibrium state of the multi-component complex system is not destroyed in the whole swelling process, thereby ensuring that the nucleation and growth of cells are very uniform during pressure release foaming.
In one embodiment, the foaming device is a non-viscous fluid polymer foam molding device.
In one embodiment, the polymer feedstock includes, but is not limited to: general plastics such as PP, PS, general engineering plastics such as PET, special engineering plastics such as PPSU; the polymer feedstock may be in the form of pellets, rods, plates or profiles.
In one embodiment, the supercritical fluid primary blowing agent is CO 2 、N 2 And inert gases.
In one embodiment, the liquid co-blowing agent is water, ethanol, n-hexane, pentane, acetone, HFO, HFC, or the like.
In a second aspect of the invention, there is provided:
a supercritical foaming method comprising the steps of:
step 1, putting a polymer raw material into a foaming device;
step 2, feeding a supercritical fluid main foaming agent into the foaming device through a constant pressure gas output device;
step 3, cooling the gaseous auxiliary foaming agent to be liquid, and then feeding the liquid auxiliary foaming agent into a foaming device through a first mass flow output device;
and step 4, swelling the supercritical fluid and the auxiliary foaming agent by the polymer raw material under the set pressure and temperature conditions, and releasing pressure to foam after reaching a homogeneous saturated state to prepare the porous foaming material.
In one embodiment, in step 3, a liquid auxiliary blowing agent is also fed into the foaming device via the second mass flow output.
In one embodiment, the liquid co-blowing agent fed into the interior of the foaming device is not in direct contact with the polymer feed when in the liquid phase.
In one embodiment, the constant pressure gas output means refers to a booster pump, a buffer tank, and a pressure reducing valve, or an ISCO pump and a buffer tank, which are connected in this order.
In one embodiment, the first mass flow output means is a mass flow pump through which the auxiliary blowing agent in the liquid bottle is injected into the foaming device in an accurately metered excess of auxiliary blowing agent.
In one embodiment, the gaseous blowing agent used to form the supercritical fluid is CO 2 、N 2 And inert gases.
In one embodiment, the liquid co-blowing agent is water, ethanol, n-hexane, pentane, acetone, HFO, HFC, or the like.
In one embodiment, the gaseous co-blowing agent may be methane or the like.
In a third aspect of the invention, there is provided:
a supercritical foaming apparatus comprising:
a first gas cylinder for storing a supercritical fluid main foaming agent; the first gas steel cylinder is connected with the foaming device through the constant-pressure gas output device;
A liquid bottle for storing a liquid co-blowing agent; the liquid bottle is connected with the foaming device;
in the foaming device, a supporting part is arranged at the bottom for placing the foaming material.
In one embodiment, the constant pressure gas output device refers to a booster pump and a buffer tank which are connected in sequence, the booster pump is connected with a first gas steel cylinder, and the first buffer tank is connected with the foaming device.
In one embodiment, the buffer tank is further provided with a heating component, and the heating component is used for heating the gas in the buffer tank; in one embodiment, the heating element is a heat trace belt.
In one embodiment, the first buffer tank is connected to the foaming device sequentially through a pressure reducing valve and a first check valve.
In one embodiment, the constant pressure gas output means is referred to as an ISCO pump.
In one embodiment, the bottom of the foaming device is further provided with porous ceramics for uniformly heating the liquid auxiliary foaming agent at the bottom.
In one embodiment, the foaming device is further connected with a back pressure valve and a gas-liquid separator in sequence; the gas-liquid separator is used for condensing the gas exhausted after foaming and performing gas-liquid separation treatment.
In one embodiment, the liquid bottles are connected to the foaming device in turn by a mass flow pump.
In one embodiment, the mass flow pump is connected to the foaming device sequentially through a second non-return valve, a foaming device liquid inlet.
In a fourth aspect of the invention, there is provided:
a supercritical foaming apparatus comprising:
a first gas cylinder for storing a supercritical fluid main foaming agent; the first gas steel cylinder is connected with the foaming device through the constant-pressure gas output device;
and the second gas steel cylinder is used for storing the gaseous auxiliary foaming agent and is connected with the foaming device through the cooling device and the second mass flow pump in sequence.
In one embodiment, the constant pressure gas output device refers to a booster pump, a buffer tank and a pressure reducing valve, or an ISCO pump and a buffer tank, which are sequentially connected. The booster pump or ISCO pump is connected with the first gas steel cylinder, and the pressure reducing valve is connected with the foaming device.
In one embodiment, the buffer tank is further provided with a heating component, and the heating component is used for heating the gas in the buffer tank; in one embodiment, the heating element is a heat trace belt.
In one embodiment, the foam-assisting agent further comprises a liquid bottle for storing a liquid foam-assisting agent; the liquid bottle is connected to the foaming device by a first mass flow pump.
In one embodiment, the first mass flow pump is connected to the foaming device through a second non-return valve.
In one embodiment, the second mass flow pump is connected to the foaming device through a third non-return valve.
In a fifth aspect of the invention, there is provided:
the supercritical foaming device is applied to the production of the foaming polymer material by a supercritical foaming method.
In one embodiment, the use is for increasing the expansion ratio of a foamed polymeric material and decreasing the foaming temperature of the material.
Advantageous effects
1. The process solves the problems of foaming uniformity and performance stability of the large-size non-viscous fluid polymer in a multi-component multi-phase complex system, and simultaneously reduces the foaming temperature of the polymer material, improves the foaming multiplying power, improves the performance of a foaming product and the like. The method is stable and high in repeatability, solves the problem of amplification effect existing in the industrialized production of the foaming material, makes the material possible to be applied to industry from laboratory results, and is suitable for amplification production.
2. By the method, the polymer material is always in the system with the maximum content of the auxiliary foaming agent, so that the polymer material can be absorbed to the upper limit of the content of the auxiliary foaming agent which can be absorbed by the polymer material, the foaming multiplying power of the polymer material can be improved to the greatest extent, the foaming temperature of the polymer material is reduced, the cell structure is more uniform, and the produced polymer material has the optimal performance.
3. The polymer material in the high-pressure container can timely supplement the main foaming agent in the high-pressure container in the process of absorbing the main foaming agent through the pressure stabilizing function of the main foaming agent and the pressure reducing valve of the buffer bottle, so that three phases (phase 1: main foaming agent (enrichment) -auxiliary foaming agent gas (auxiliary), phase 2: liquid auxiliary foaming agent (enrichment) -main foaming agent (auxiliary), and phase 3: polymer (enrichment) -main foaming agent (auxiliary) -auxiliary foaming agent phase (auxiliary)) in the high-pressure container are always in dynamic balance, the gas self-regulating function is achieved, and conditions are created for stably producing products with better performance.
4. The liquid pump is used for conveying excessive liquid auxiliary foaming agent, so that the auxiliary foaming agent which is deposited at the bottom can be continuously supplemented with the auxiliary foaming agent which is consumed by the polymer due to the absorption of the mixed foaming agent, the three phases in the foaming device are ensured to be in dynamic balance, and conditions are created for stably producing products with better performance.
The process of the invention has wide technological parameter range, basically can meet the industrial requirement, the pressure can reach the highest pressure-resistant value (the highest pressure-resistant value of the high-pressure container in the example is 35 MPa) from the lowest pressure capable of conveying gas to the high-pressure container, the temperature can reach the highest temperature range capable of being used by the high-pressure container (the high-pressure container used in the example can resist the temperature of 300 ℃), the swelling time is determined according to the required production materials, and the pressure release time can be controlled manually or automatically by a computer.
Drawings
Fig. 1 is a diagram of the apparatus of the present invention.
Fig. 2 is a diagram of another apparatus of the present invention.
FIG. 3 is an SEM photograph of a foamed material prepared in example 1.
Fig. 4 is an SEM photograph of the foaming material prepared in the control experiment 1.
Fig. 5 is an SEM photograph of the foaming material prepared in the control experiment 2.
Fig. 6 is an SEM photograph of the foaming material prepared in example 2.
Fig. 7 is an SEM photograph of the foaming material prepared in the control experiment 3.
Fig. 8 is an SEM photograph of the foaming material prepared in the control experiment 4.
FIG. 9 is the change in the index of the PP+n-hexane (excess non-stabilized) high pressure vessel pressure gauge in swelling.
FIG. 10 is an indication of the change in swelling of a PPSU+distilled water (excess non-stabilized) high pressure vessel pressure gauge.
Fig. 11 is a multicomponent phase diagram.
Wherein, 1, a first gas steel cylinder; 2. a liquid bottle; 3. a booster pump; 4. a first mass flow pump; 5. a buffer tank; 6. a heating member; 7. a pressure reducing valve; 8. a first non-return valve; 9. a foaming device liquid inlet; 10. a porous ceramic; 11. a foaming device; 12. a back pressure valve; 13. a gas-liquid separator; 14. a second non-return valve; 15. a support member; 16. a foaming device liquid inlet; 17. a second gas cylinder; 18. a cooling device; 19. a second mass flow pump; 20. and a third check valve.
Detailed Description
The invention provides a supercritical foaming method and a device for stably preparing a foaming product by self-adjustment under a multiphase and multicomponent complex system. The method utilizes the synergistic foaming action of the main foaming agent and the auxiliary foaming agent, wherein the main foaming agent can be foaming agent common in the prior supercritical foaming, such as CO 2 、N 2 Etc.; the auxiliary foaming agent has the functions of assisting the main foaming agent to dissolve into a polymer matrix, plasticizing polymer material further, reducing the glass transition temperature of the polymer material, widening the foaming temperature range, and improving the foaming ratio of the polymer, and can be water, ethanol, n-hexane, pentane, acetone, HFO, HFC and the like.
The foaming material to be prepared in the present invention may be a material that can be prepared by a supercritical foaming method in the prior art, mainly a polymer material, including but not limited to: general plastic such as PP, PS, general engineering plastic such as PET, special engineering plastic such as PPSU. The material may be in the form of pellets, bars, plates or profiles.
In the prior art, the main foaming agent and the auxiliary foaming agent are added into the foaming equipment at the same time, and the proportion of the main foaming agent and the auxiliary foaming agent is unstable in the actual foaming process due to the influence of a plurality of factors such as the addition amount and the permeation rate of the main foaming agent and the auxiliary foaming agent in the foaming process, so that a multi-component complex system in a polymer is unstable in the swelling process, the foaming behavior is poor, and the foam uniformity and the performance stability of the foaming material are poor.
According to the technical scheme, firstly, excessive auxiliary foaming agent is injected into the foaming equipment, when the auxiliary foaming agent is in a liquid state in the injection process, the auxiliary foaming agent with the accurate content which is 2-5 times of the content of the absorbable auxiliary foaming agent of the polymer is conveyed into a high-pressure container cavity through a mass flow pump, and the liquid level of the liquid auxiliary foaming agent is lower than that of the polymer raw material in the process; then, supercritical gas (CO) is supplied by a booster pump 2 、N 2 Etc.) is conveyed into a high-pressure buffer tank (0-40 MPa) at a set pressure, then the gas in the high-pressure buffer tank is quickly conveyed into a high-pressure container cavity through a pressure reducing valve, the booster pump and the buffer tank have the functions of providing supercritical fluid supply with stable pressure, and meanwhile, the buffer tank also has the function of quickly conveying supercritical gas to quickly stabilize the internal system of the foaming device. The main foaming agent and the auxiliary foaming agent enter the high-pressure container cavity through the one-way valve, and then the sample in the high-pressure container cavity is subjected to set process conditions (temperature, pressure and the like).
Because the auxiliary foaming agent has certain vapor pressure under the set pressure and temperature conditions, a part of auxiliary foaming agent still keeps liquid state in the swelling process, and a small amount of auxiliary foaming agent is dissolved in the auxiliary foaming agent to form auxiliary foaming agent (enrichment) -main foaming agent (less) phase which is deposited at the bottom of the high-pressure container; the other part is evaporated into a gaseous state and forms a swelling polymer of a main foaming agent (enrichment) auxiliary foaming agent (less) phase together with the main foaming agent; since the polymer is not in contact with the "auxiliary blowing agent (rich) -blowing agent (few) phase", the "main blowing agent (rich) -auxiliary blowing agent (few) phase" penetrates into the polymer under the set process conditions, forming the "polymer (rich) -main blowing agent (few) -auxiliary blowing agent (few) phase" inside the polymer. Along with the continuous diffusion of the main foaming agent and the auxiliary foaming agent into the sample, the main foaming agent can be continuously injected into the cavity of the high-pressure container through the pressure reducing valve with the pressure stabilizing function, the auxiliary foaming agent is excessively present at the bottom of the cavity of the high-pressure container, the swelling process can be stabilized through phase balance self-adjustment (when the gaseous auxiliary foaming agent dissolved in the main foaming agent is excessively present, the gaseous auxiliary foaming agent is converted into a liquid state under certain conditions of temperature and pressure and is deposited on the lower liquid layer of the foaming device due to phase separation, and when the consumption speed of the gaseous auxiliary foaming agent dissolved in the main foaming agent is excessively high, part of the liquid auxiliary foaming agent deposited at the bottom of the high-pressure container is converted into a gaseous state under the condition of pressure and temperature, and the gaseous partial pressure of the auxiliary foaming agent is maintained again). The excessive auxiliary foaming agent can ensure that the polymer material is always under the maximum auxiliary foaming agent content, the polymer material absorbs the maximum auxiliary foaming agent content, and in the process of absorbing the auxiliary foaming agent by the polymer material, the auxiliary foaming agent (enrichment) -main foaming agent (less) phase is in dynamic balance because the auxiliary foaming agent can be continuously provided, when the auxiliary foaming agent content deposited at the bottom is reduced due to consumption, part of the dissolved main foaming agent is returned to the main foaming agent (enrichment) -auxiliary foaming agent (less) phase and then enters the polymer, and the stability of the foaming material is ensured by multi-component multi-phase self-balancing. During foaming, the polymeric foam material should not be directly contacted with the liquid co-blowing agent, but rather in a homogeneous system of the primary and co-blowing agents, so that the co-blowing agent maintains a constant dosage concentration throughout the process.
Through the self-balancing process, the pressure relief foaming after the homogeneous saturated state is achieved under the multi-component complex system (polymer component, supercritical fluid component and auxiliary foaming agent component) is realized. The phase diagram of the above process is shown in fig. 11.
In the above method, the main foaming agent should be fed into the foaming device in a constant pressure manner, and in order to achieve the above object, the pressure of the main foaming agent for stable supply is maintained, and in the method provided by the present invention, this function may be achieved in various manners:
1. booster pump-buffer tank scheme: the booster pump conveys supercritical foaming fluid into the high-pressure buffer tank at a set pressure, then the supercritical fluid in the high-pressure buffer tank is rapidly conveyed into the high-pressure container cavity through the pressure reducing valve, the pressure of the supercritical fluid can be stabilized through the pressure reducing valve, so that the system is always in a dynamic balance state in the process of absorbing the supercritical fluid by the polymer material, when the supercritical fluid is absorbed by the polymer, the buffer tank can provide the required supercritical fluid through the pressure reducing valve, and when the pressure in the buffer tank is lower than the set value, the booster pump can provide gas for the buffer tank, so that the effect of supercritical fluid self-adjustment is achieved.
2. ISCO pump scheme: the ISCO pump is used for replacing the booster pump and the pressure reducing valve, the ISCO pump can compress gas into the pump firstly, then the gas can be automatically pressurized in the pump, and the gas can be quickly conveyed into the buffer tank after reaching the set pressure, so that the effect of the booster pump is achieved; when the delivery volume reaches the set pressure, the system is unstable due to the reduction of the foaming agent due to the absorption of the foaming agent by the material, and the like, and the second function of the ISCO pump, namely the pressure stabilizing function, plays a role in continuously providing the supercritical fluid to keep the system in the high-pressure container stable.
In the above embodiments, the method is mainly suitable for polymer foaming operation (for example, liquid such as ethanol) by using a liquid auxiliary foaming agent, but in other cases, polymer foaming operation is performed by using a gaseous auxiliary foaming agent or a plurality of mixed foaming agents, and in the case of using a gaseous auxiliary foaming agent or a plurality of mixed foaming agents, the method provided by the invention can connect the gaseous auxiliary foaming agent with the foaming device through a second mass flow output device as shown in fig. 2, in this way, the polymer foaming raw material in the foaming device is not required to be isolated from the liquid auxiliary foaming agent any more, and the constant adding amount of the gaseous auxiliary foaming agent is controlled by a mass flow pump mode.
Based on the method, the device provided by the invention is as follows:
in one embodiment, the device used in the present invention is shown in FIG. 1.
Comprising the following steps:
a first gas cylinder 1 for storing a supercritical fluid main foaming agent; the first gas steel cylinder 1 is connected with the foaming device 11 through a constant-pressure gas output device;
a liquid bottle 2 for storing a liquid auxiliary foaming agent; the liquid bottle 2 is connected to the foaming device 11;
in the foaming device 11, a support member 15 is provided at the bottom for placing the foaming material. The foaming device 11 is a high-pressure container, and is a place where the polymer material is subjected to foaming experiments, and provides stable temperature and pressure environments to enable the polymer material and the mixed foaming agent to be in a homogeneous system;
in one embodiment, the constant pressure gas output device refers to a booster pump 3 and a buffer tank 5 which are sequentially connected, the booster pump 3 is connected to a first gas cylinder 1, and the first buffer tank 5 is connected to a foaming device 11. The booster pump is used to provide a stable pressure to deliver the gas phase into the buffer tank. The gas with the required specific pressure is conveyed into the buffer tank through the several times of conveying of the booster pump, and then the gas in the bottle is quickly conveyed into the foaming device, so that the inside of the foaming device is in the set process condition as soon as possible, and the process is more stable
In one embodiment, the buffer tank 5 is further provided with a heating component 6, and the heating component 6 is used for heating the gas in the buffer tank 5; in one embodiment, the heating element 6 is a heat trace belt. The heat tracing belt heats the high-pressure buffer tank, and the foaming temperature in the high-pressure container is required to avoid the temperature reduction in the cavity of the high-pressure container after the low-temperature foaming agent is added into the foaming device
In one embodiment, the first buffer tank 5 is connected to the foaming device 11 through a pressure reducing valve 7 and a first non-return valve 8 in sequence. The pressure reducing valve stabilizes the pressure of the gas and ensures that the gas in the high-pressure container is always under the function of the set pressure; the check valve prevents the mixed gas from flowing back into the buffer tank when the pressure in the kettle is higher than that in the buffer tank.
In one embodiment, the constant pressure gas output means is referred to as an ISCO pump. The ISCO pump is used to replace the booster pump and the pressure reducing valve, and the ISCO pump can form self-adjustment of the addition amount of the main foaming agent and the gas auxiliary foaming agent. When the pressure is increased due to excessive gas in the cavity of the high-pressure container, the pressure stabilizing function of the ISCO pump enables the gas to return to the ISCO pump through the high-pressure buffer tank; when the polymer material absorbs the foaming agent, the ISCO pump can continuously supply gas, so that the system in the high-pressure container is always in a stable state, and the ISCO pump plays a role of a pressure reducing valve and thus plays a role of self-regulating gas. The liquid co-blowing agent phase is in excess in the high pressure vessel relative to the amount of co-blowing agent that the polymeric material is capable of absorbing, excess liquid co-blowing agent is deposited at the bottom of the high pressure vessel, excess co-blowing agent enters the "polymeric material (rich) -blowing agent (less) -co-blowing agent (less)" homogeneous system from the liquid pool when the polymeric material absorbs the liquid co-blowing agent, and excess co-blowing agent is deposited from the system into the liquid co-blowing agent pool when the "polymeric material (rich) -main blowing agent (less) -co-blowing agent (less)" system is in excess, thereby ensuring stability of the system.
In one embodiment, the bottom of the foaming device 11 is further provided with a porous ceramic 10, so that the liquid auxiliary foaming agent at the bottom is uniformly heated.
In one embodiment, the foaming device 11 is also connected with the gas-liquid separator 13 through the back pressure valve 12 in sequence; the gas-liquid separator 13 is used for condensing the gas exhausted after foaming and performing gas-liquid separation treatment. The back pressure valve prevents the mixed blowing agent from flowing back, maintaining a constant pressure at the outlet. The gas-liquid separator 13 is used as a recovery system, is connected with an air outlet valve of the high-pressure container, recovers the mixed foaming agent, controls the pressure and the temperature in the recovery bottle to separate the gas from the liquid, and recovers the auxiliary foaming agent for recycling in the following foaming experiment.
In one embodiment, the liquid bottles 2 are in turn connected to a foaming device 11 via a mass flow pump 4. The mass flow pump delivers an accurately metered liquid co-blowing agent phase to the foaming device.
In one embodiment, the mass flow pump 4 is connected to the foaming device 11 via a second non-return valve 14, in turn, the foaming device liquid inlet 9.
In another embodiment, the device used in the present invention is shown in FIG. 2.
Comprising the following steps:
a first gas cylinder 1 for storing a supercritical fluid main foaming agent; the first gas steel cylinder 1 is connected with the foaming device 11 through a constant-pressure gas output device;
A second gas cylinder 17 for storing a gaseous auxiliary blowing agent, the second gas cylinder 17 being connected to the blowing device 11 in turn via a cooling device 18 and a second mass flow pump 19.
The constant-pressure gas output device is characterized in that a booster pump 3, a buffer tank 5 and a pressure reducing valve 7 are sequentially connected, the booster pump 3 is connected with the first gas steel cylinder 1, and the pressure reducing valve 7 is connected with the foaming device 11.
The buffer tank 5 is also provided with a heating component 6, and the heating component 6 is used for heating the gas in the buffer tank 5; in one embodiment, the heating element 6 is a heat trace belt.
A liquid bottle 2 for storing a liquid auxiliary foaming agent; the liquid bottle 2 is connected to the foaming device 11 by means of a first mass flow pump 4.
The first mass flow pump 4 is connected to the foaming device 11 via a second non-return valve 14.
The second mass flow pump 19 is connected to the foaming device 11 via a third non-return valve 20.
In such an implementation as in fig. 2, simultaneous addition of gaseous co-blowing agent and liquid co-blowing agent may be achieved. The porous foaming material is prepared by pressure relief foaming after reaching a homogeneous saturated state under a multi-component complex system (polymer component, supercritical fluid component, gaseous auxiliary foaming agent component and liquid auxiliary foaming agent component).
In either of the modes of fig. 1 or 2, the specific type of foaming device 11 is not limited. The device is suitable for solid foaming molding of all non-viscous polymers.
Example 1
As shown in FIG. 1, using the polypropylene foamed polymer material production as an example, polypropylene (raw material in the form of a block, about 600 cm m 2 samples in size) was first introduced into a high-pressure vessel (volume of about 5L) and a liquid was usedThe bulk pump delivers excess n-hexane to the high pressure vessel through the heated buffer tank while the high pressure vessel is warmed to 140℃and 15 MPa CO is pumped using the ISCO pump 2 The gas is delivered into a high-pressure container through a heated buffer tank, the ISCO pump is kept in an on state, the pressure in the container is stabilized, and the polymer is filled with CO 2 And n-hexane for 5 hours, allowing the polymer to fully absorb CO 2 And n-hexane, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation; the results of foaming ratio and the like of the obtained foam material after foaming are shown in table 1.
Control experiment 1
The differences from example 1 are: ISCO pumps only provide a delivery function, unstable pressures.
Taking polypropylene foamed polymer material production as an example, polypropylene is first added to a high pressure vessel, excess n-hexane is transferred to the high pressure vessel through a heated buffer tank by means of a liquid pump, while the high pressure vessel is warmed to 140℃and 15 MPa CO is transferred by means of an ISCO pump 2 The gas is delivered to the high pressure vessel through the heated buffer tank, the ISCO pump is turned off, and the polymer is filled with CO 2 And n-hexane for 5 hours, allowing the polymer to fully absorb CO 2 And n-hexane, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation.
Control experiment 2
The differences from example 1 are: the auxiliary blowing agent is continuously fed by a common liquid pump during the swelling process, rather than being excessively added to the bottom of the high-pressure container in advance.
Taking polypropylene foamed polymer material production as an example, polypropylene is first added into a high pressure vessel, the high pressure vessel is warmed to 140 ℃, and 15 MPa CO is pumped by an ISCO pump 2 The gas is delivered to the high pressure vessel through the heated buffer tank, maintaining the ISCO pump in an on state, stabilizing the pressure within the high pressure vessel. In swelling In the process of (2), normal hexane is continuously conveyed into a high-pressure container through a heated buffer tank by using a common liquid pump, and the polymer is filled with CO 2 And n-hexane for 5 hours, allowing the polymer to fully absorb CO 2 And n-hexane, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation.
Table 1 PP foaming parameters of the foaming of the n-hexane auxiliary foamer under different conditions (140 ℃,15MPa, 5 hours of swelling)
As can be seen from Table 1, under the same process conditions, the pore size and the foam density of the foam obtained by the non-stabilized foaming are slightly smaller than those of the foam obtained by the stabilized foaming, and although the foaming magnification measured by the non-stabilized foaming is larger than that of the foam obtained by the stabilized foaming, a lot of foam cracks can be seen in the SEM image (figure 4), one foam is broken into a lot of small holes, the overall foam appearance is quite optimistic, while the SEM image (figure 3) of the inverted stabilized foaming has quite uniform foam and quite good overall appearance. As can be seen from fig. 7, the gauge number was varied slowly throughout the swelling process, and this pressure instability was one of the main reasons for the formation of the cell morphology shown in the SEM images.
It can be seen from the table that under the same process conditions, the cell size and the expansion ratio of the foaming sample obtained by continuously feeding the auxiliary foaming agent are far smaller than those of the foaming product mixed with the excessive auxiliary foaming agent, and the SEM image (fig. 5) also shows the foaming product. The foaming rate of the PP is improved and the foaming temperature of the PP is reduced due to the fact that the auxiliary foaming agent is continuously conveyed in the swelling process and plays a role in cooperation with the foaming agent, but the main foaming agent and the auxiliary foaming agent cannot be guaranteed to be always in a stable homogeneous state in the continuous conveying process, and meanwhile, the polymer material cannot be guaranteed to be in the maximum mixed foaming agent content, so that a good effect is not achieved. It is seen from the SEM images that many white small areas are just areas where PP crystallizes, and their presence limits the increase of the foaming magnification, indicating that this process condition does not well reduce the foaming temperature of PP, so that the foaming temperature of 140 ℃ is still below the melting point of PP.
Example 2
Taking the production of polyphenylsulfone foaming polymer material as an example, firstly, the polyphenylsulfone raw material is in the shape of block, the size is about 600 cm m, 2 samples are added into a high-pressure container (the volume is about 5L), the temperature of a heat tracing belt on the high-pressure container and a buffer bottle is set to be the temperature required by foaming, excessive distilled water is conveyed into the high-pressure container through the buffer bottle by a liquid pump, and the CO of 20MPa is conveyed by a booster pump 2 The gas is delivered into a high-pressure container through a high-pressure buffer bottle, the pressure of the high-pressure container is stabilized by a pressure reducing valve, and the PPSU is filled with CO 2 Swelling in distilled water for 5 hr to allow PPSU to fully absorb CO 2 And distilled water, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation; the results of foaming ratio and the like of the obtained foam material after foaming are shown in Table 2.
Control experiment 3
The differences from example 1 are: ISCO pumps only provide a delivery function, unstable pressures.
Taking the production of polyphenylsulfone foaming polymer material as an example, polyphenylsulfone is firstly added into a high-pressure container, the temperature of a heat tracing belt on the high-pressure container and a buffer bottle is set to be required by foaming, excessive distilled water is conveyed into the high-pressure container through the buffer bottle by a liquid pump, and CO of 20 MPa is conveyed by a booster pump 2 The gas is delivered into the high-pressure container through the high-pressure buffer bottle, the pressure reducing valve is closed, the pressure in the high-pressure container is not stabilized, and the PPSU is filled with CO 2 Swelling in distilled water for 5 hr to allow PPSU to fully absorb CO 2 And distilled water, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation.
Control experiment 4
The differences from example 1 are: the auxiliary blowing agent is continuously fed by a common liquid pump during the swelling process, rather than being excessively added to the bottom of the high-pressure container in advance.
Taking the production of polyphenylsulfone foaming polymer material as an example, polyphenylsulfone is firstly added into a high-pressure container, the temperature of a heat tracing belt on the high-pressure container and a buffer bottle is set to be the temperature required by foaming, and a booster pump is used for putting CO of 20 MPa 2 The gas is delivered into the high-pressure container through the high-pressure buffer bottle, and the pressure of the high-pressure container is stabilized by the pressure reducing valve. In the swelling process, distilled water is continuously conveyed into a high-pressure container through a buffer tank by using a common liquid pump, and the PPSU is filled with CO 2 Swelling in distilled water for 5 hr to allow PPSU to fully absorb CO 2 And distilled water, then opening a valve for 2 seconds to release pressure, recycling the mixed foaming agent into a recycling device, and re-extracting the auxiliary foaming agent from the mixed foaming agent by using the recycling device for next experimental operation.
TABLE 2 foaming parameters of PPSU foaming with Water-assisted foaming agent under different conditions (190 ℃,20 MPa, 5 h swelling)
It can be seen from table 2 that under the same process conditions, the pore diameter, the foaming density and the foaming ratio of the foam obtained by the non-stabilized foaming are slightly smaller than those of the foam obtained by the stabilized foaming, and as can be seen in fig. 7, the phenomenon of big and small pores also occurs in the non-stabilized foaming process, the positions of the big and small pores are very uneven, and meanwhile, the phenomenon of breaking pores also occurs, the overall appearance is poor, and as can be seen in the SEM image of the stabilized foaming, the foam pores are very uniform, and the overall appearance is very good (fig. 6). As can be seen from the variation of the gauge number in fig. 10, the gauge number is always slowly varying without stabilizing the pressure, and this pressure instability is one of the main reasons for the formation of the cell morphology shown in the SEM images.
It can be seen from table 2 that the foam sample obtained by continuously feeding the auxiliary foaming agent has smaller cell size and foaming ratio than the foam product mixed with the excessive auxiliary foaming agent under the same process conditions, and can also be seen from the SEM image (fig. 8). The foaming rate of the PPSU is improved and the foaming temperature of the PPSU is reduced due to the fact that the auxiliary foaming agent is continuously conveyed in the swelling process and the foaming agent are synergistically acted, but the main foaming agent and the auxiliary foaming agent cannot be guaranteed to be always in a stable homogeneous state in the continuous conveying process, and meanwhile, the polymer material cannot be guaranteed to be under the maximum mixed foaming agent content, so that a good effect is not achieved. So that the foaming ratio and the pore size of the product are smaller than those of the product under the condition of excessive auxiliary foaming agent.
Claims (9)
1. A multiphase, multicomponent, self-regulating supercritical fluid foaming process comprising the steps of:
step 1, putting a polymer raw material into a foaming device;
step 2, injecting excessive liquid auxiliary foaming agent into the foaming device, and simultaneously ensuring that the liquid auxiliary foaming agent is not directly contacted with the polymer raw material when in a liquid phase state;
Step 3, supplying a main supercritical fluid foaming agent into the foaming device through a constant pressure output system to enable the foaming device to be at a set temperature and pressure;
step 4, swelling the supercritical fluid main foaming agent and the auxiliary foaming agent by the polymer raw material under the set pressure and temperature conditions, conveying the supercritical fluid main foaming agent with the set pressure and the pressure stabilizing function of the constant pressure output system through the constant pressure output system, and buffering the constant pressure output system to timely supplement the supercritical fluid main foaming agent in the foaming device in the process of absorbing the supercritical fluid main foaming agent by the polymer material in the foaming device, wherein the temperature and the pressure of the foaming device are constant so that the proportion of the supercritical fluid main foaming agent to the auxiliary foaming agent in the supercritical fluid enrichment phase is unchanged; and (5) releasing pressure and foaming after reaching a homogeneous saturated state to prepare the porous foaming material.
2. The multi-phase multi-component self-regulating supercritical fluid foaming method according to claim 1, wherein after the foaming in the step 4 is completed, the gas in the foaming device is discharged, after cooling, the auxiliary foaming agent is condensed into a liquid state, gas-liquid separation is carried out, and the liquid auxiliary foaming agent and the supercritical fluid main foaming agent are recovered.
3. The multiphase, multicomponent, self-regulating supercritical fluid foaming process of claim 1, wherein the constant pressure output system is: the device comprises a booster pump, a buffer tank and a pressure reducing valve which are connected in sequence, wherein the pressure of the foaming device is stabilized by the pressure reducing valve, or an ISCO pump and the buffer tank which are connected in sequence are utilized, and the ISCO pump is kept in an opening state;
Heating treatment is needed before the supercritical gas main foaming agent is supplied into the foaming device; the foaming device is suitable for foaming the non-sticky polymer, and the non-sticky polymer raw material is granules, bars or plates.
4. The multiphase, multicomponent, self-regulating supercritical fluid foaming process of claim 1, wherein the polymer feedstock comprises: PP, PS, PET or PPSU; the main foaming agent of the supercritical fluid is CO 2 Or N 2 The method comprises the steps of carrying out a first treatment on the surface of the The liquid co-blowing agent is water, ethanol, n-hexane, pentane, acetone, HFO or HFC.
5. A supercritical foaming apparatus for use in the multiphase, multicomponent, self-regulating supercritical fluid foaming process of claim 1, comprising:
a first gas cylinder (1) for storing a supercritical fluid main foaming agent; the first gas steel cylinder (1) is connected with the foaming device (11) through a constant-pressure gas output device;
a liquid bottle (2) for storing a liquid co-foaming agent; the liquid bottle (2) is connected with the foaming device (11);
in the foaming device (11), a supporting part (15) is arranged at the bottom for placing foaming materials;
a space for the auxiliary foaming agent enrichment phase is reserved in the foaming device, and the polymer material is not contacted with the auxiliary foaming agent enrichment phase when being placed on the space.
6. The supercritical foaming device according to claim 5, wherein the constant-pressure gas output device is a booster pump (3) and a buffer tank (5) which are connected in sequence, the booster pump (3) is connected with the first gas steel cylinder (1), and the buffer tank (5) is connected with the foaming device (11); the buffer tank (5) is also provided with a heating component (6), and the heating component (6) is used for heating the gas in the buffer tank (5); the heating component (6) is a heat tracing belt.
7. Supercritical foaming device according to claim 6, characterized in that the buffer tank (5) is connected to the foaming device (11) in turn through a pressure reducing valve (7) and a first non-return valve (8).
8. The supercritical foaming apparatus according to claim 5, wherein the constant pressure gas output means is an ISCO pump.
9. Supercritical foaming device according to claim 8, characterized in that the bottom of the foaming device (11) is further provided with porous ceramics (10) for uniformly heating the liquid auxiliary foaming agent at the bottom; the foaming device (11) is also connected with a gas-liquid separator (13) through a back pressure valve (12) in sequence; the gas-liquid separator (13) is used for condensing the gas exhausted after foaming and performing gas-liquid separation treatment; the liquid bottle (2) is connected with the foaming device (11) through the first mass flow pump (4) in sequence; the first mass flow pump (4) is connected to the foaming device (11) through a second non-return valve (14) and the foaming device liquid inlet (9) in sequence.
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| CN113733352B (en) * | 2021-04-08 | 2022-08-16 | 中国矿业大学 | Method and device for preparing foam concrete by using supercritical carbon dioxide |
| CN114311487A (en) * | 2022-02-21 | 2022-04-12 | 山东大学 | Polymer supercritical fluid mixing foaming system and method |
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| CN110480913A (en) | 2019-11-22 |
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