WO2019024868A1 - 热塑性微气囊聚合物弹性体材料及其制备 - Google Patents

热塑性微气囊聚合物弹性体材料及其制备 Download PDF

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Publication number
WO2019024868A1
WO2019024868A1 PCT/CN2018/098024 CN2018098024W WO2019024868A1 WO 2019024868 A1 WO2019024868 A1 WO 2019024868A1 CN 2018098024 W CN2018098024 W CN 2018098024W WO 2019024868 A1 WO2019024868 A1 WO 2019024868A1
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Prior art keywords
pressure
polymer
thermoplastic
process water
polymer material
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PCT/CN2018/098024
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English (en)
French (fr)
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陈乔健
郭杨龙
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南通德亿新材料有限公司
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Priority to US16/636,340 priority Critical patent/US20200165401A1/en
Priority to EP18840917.1A priority patent/EP3663358B1/en
Publication of WO2019024868A1 publication Critical patent/WO2019024868A1/zh

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    • C08J2475/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to the field of preparation of polymer materials, in particular to a thermoplastic micro-balloon polymer elastomer material and preparation thereof.
  • Thermoplastic polymer elastic materials are widely used in the manufacture and use of facilities, equipment, tools and consumables. With the development of society, environmental protection, energy saving, and consumption reduction, the demand for lightweight materials has become more and more urgent.
  • Thermoplastic polymer elastomers have also begun to be lightweight and experimental and validated and continue to be applied. For example, polypropylene PP foaming, polyethylene PE foaming, polystyrene PS foaming, polyester PET foaming, polyamide PA foaming, and polyurethane TPU foaming, and the like.
  • thermoplastic polymer elastomers include: puffing in a casting mold, injection puffing, extrusion puffing, and puffing in an autoclave.
  • the foaming uniformity and foaming ratio of injection foaming are poor, and the extruded foamed material is easily melted and broken, resulting in cell breakdown and surface collapse.
  • the foaming in the autoclave has high safety risk and low productivity.
  • the principle of foaming it is divided into: physical foaming and chemical foaming. No matter which kind of polymer raw material is selected, no matter which kind of foaming method is adopted, the foaming process generally has to go through the stages of forming bubble nuclei ⁇ bubble core expansion ⁇ bubble solidification setting.
  • thermoplastic polymer elastic material still needs to retain good physical properties after foaming and puffing, which requires design of the material structure and material cells after puffing.
  • the existing foamed granules and the like are generally prepared by using a single polymer raw material and a foaming agent under a puffing process.
  • the foamed particles having a stable structure and not collapsed are basically pure closed pore structures of continuous skin.
  • the foamed particles of the cell structure have high support strength, since the skin is continuous, the internal gas cannot be discharged under pressure.
  • the foamed particles are hard to the touch, and such closed-cell structure particles are substantially difficult to achieve positive feedback when pressed, and therefore, slippage is likely to occur when used on a shoe article.
  • the control method of the expanded thermoplastic polymer elastic material at home and abroad is simple and unstable, so that, in particular, such as nylon, PET, PPT, thermoplastic polyurethane, etc., there are few stable and controllable expansion cases in material properties and processing techniques.
  • thermoplastic micro-balloon polymer elastomer material and a method of making the same in order to overcome the deficiencies of the prior art described above.
  • thermoplastic micro-balloon polymer elastomer material comprising the following components by weight: 0.1-97% of the support skeleton polymer material, 0.1-97 of the pressure-resistant slow-rebound polymer material %, nucleating agent 0.01 to 0.5%, foaming agent 0.1 to 10%.
  • the support matrix polymer material is a high molecular weight, high hardness, high crystalline or high polarity polymer material, and the pressure resistant slow rebound polymer material is in contact with the support matrix polymer material.
  • the support matrix polymer material is a high molecular weight, high hardness, high crystalline or high polarity polymer material
  • the pressure resistant slow rebound polymer material is in contact with the support matrix polymer material.
  • the support skeleton polymer material is a high molecular weight polyurethane
  • the corresponding pressure-resistant slow rebound polymer material is a low molecular weight polyurethane
  • the support skeleton polymer material is a high-hardness thermoplastic polymer elastomer (which may be selected according to actual conditions such as TPU, TPE or rubber, etc.), and the corresponding pressure-resistant slow-rebound polymer material is low-hardness thermoplastic polymer elasticity. body;
  • the support skeleton polymer material is polyamide or polyester, and the corresponding pressure-resistant slow rebound polymer material is thermoplastic polyurethane.
  • the high molecular weight polyurethane has a molecular weight Mw of from 8 ⁇ 10 4 to 5 ⁇ 10 5 and a molecular weight M w of the low molecular weight polyurethane of from 2 ⁇ 10 4 to 2.5 ⁇ 10 5 . .
  • the high hardness thermoplastic polymer elastomer has a Shore hardness of 80 A to 75 D
  • the low hardness thermoplastic polymer elastomer has a Shore hardness of 30 to 85 A.
  • Low hardness two thermoplastic polymer elastomers are generally selected from the same substance.
  • the polyester or polyamide is a modified low melting point polyester or a modified low melting point polyamide, respectively, and controls the melting point of the support skeleton polymer material and the pressure resistant rebound polymer material. The difference is within 20 °C. More preferably, the modified low melting point polyester may be selected such as modified PET, PTT, PBT, etc., and the modified low melting point polyamide may be modified as low melting point PA6, PA6I, PA11, PA12, PA9 and the like.
  • the nucleating agent is selected from at least one of carbon nanotubes, silica, talc, modified calcium carbonate, carbon black or tetrafluoroethylene powder;
  • the blowing agent is at least one selected from the group consisting of CO 2 , N 2 , n-butane, n-pentane or isopentane.
  • the polymeric elastomer material has a particle size of from 0.6 to 25 mm.
  • thermoplastic micro-balloon polymer elastomer material of the present invention can be selectively added to other functional additives such as light stabilizers and antioxidants on the basis of the above-mentioned basic formula according to the requirements of the properties of the materials to be produced.
  • thermoplastic micro-balloon polymer elastomer material of one of the above purposes can be prepared by a conventional foaming process (such as kettle foaming, etc.) on the basis of its formulation, and the object of the present invention is also that, in addition to the conventional foaming process, A new method for preparing a thermoplastic microsphere polymer elastomer material as described above is further proposed, comprising the steps of:
  • the temperature of the twin-screw extruder in step (1) is 160-300 ° C
  • the twin-screw extruder length-to-diameter ratio is 32-56;
  • the temperature in the static mixer is set to 120-280 ° C
  • the inlet pressure of the melt pump is 50-200 bar
  • the difference between the hot melt pressure extruded through the die and the pressure of the process water in the underwater pelletizing chamber is controlled. 70-120 bar.
  • the process water temperature in the underwater pelletizing chamber in step (2) is 10-90 ° C, the pressure is 4-15 bar;
  • the pelletizing When the pelletizing is carried out by the process water, it is transported through a multi-stage pressure-release expansion process water pipeline which is gradually reduced in pressure at various stages.
  • the multi-stage pressure release expansion process water line in the step (2) is a four-stage process water line, wherein the water pressure of the first stage process water line is maintained and the process of entering the underwater pelletizing chamber The water pressure is consistent. More preferably, the water pressure of the first-stage process water line is 4-15 bar, the water pressure of the second-stage process water line is 3-10 bar, and the water pressure of the third-stage process water line is 2-6 bar, the fourth-stage process The water line has a water pressure of 1-4 bar.
  • the twin-screw extruder drives the twin-screw extruder at a speed of 50-900 rpm under the driving of the motor, and the setting temperature of the extruder of the extruder is preferably 160-300 ° C to ensure the thermoplastic polymer can Fully hot melted, the polymer and nucleating agent are fed from the front screw feed port, and the blowing agent is fed from the screw feed port in the middle section. After mixing, under the heating of the extruder and the shearing force of the screw, the materials are hot melted and mixed into the static mixer after the screw is fully mixed. The melt is further homogenized and cooled in the static mixer to ensure the melt temperature.
  • the inlet pressure of the melt pump is set to be between 50 and 200 bar to control the melt pressure in the screw of the extruder, and the hot melt of the mixed foaming agent and the nucleating agent is obtained.
  • the mixture is thoroughly mixed and homogenized in a controlled high pressure environment.
  • the high pressure hot melt is stably pushed into the extruder die by the melt pump pressure control and quantitative transfer function.
  • the die is a porous orifice structure with a uniform heating inside to ensure that the hot melt can stably pass through the die.
  • the hot melt sent by the high pressure of the melt pump is cut into the granules of the beans by the high-speed rotating dicing knife in the underwater granulation chamber through the respective holes of the die, and the dicing knife of the underwater dicing chamber is actually cutting the heat under water.
  • Melt Preferably, the process water of 10 to 90 ° C generates a pressure of 4 to 15 bar under the action of the process water pump, and enters the underwater pelletizing chamber through the process water inlet pipe of the pelletizing water chamber, so that the high pressure hot melt is rapidly cooled under the high pressure process water and It is cut into pellets by a pelletizing knife.
  • the pressure difference can be adjusted by the inlet pressure of the melt pump and the pressure of the variable frequency process water pump, the initial expansion rate of the polymer which is cut into pellets in the whole process And the rate is controllable and stable. Because the cooling time of the freshly cut granular polymer is very short and the crystallization speed of the material in different formulations is very different, it is particularly preferred in the present process to design a multi-stage pressure-release expansion process water pipeline, using the outer skin of the granular polymer in the process.
  • the granulated melt partially cools and pre-expands in the presence of a pressure differential.
  • the water pressure is reduced to 3 to 10 bar by increasing and shortening the diameter of the pipeline, and at this time, the granular melt is further cooled, and the strength of the outer surface is increased but the pressure difference is increased to re-expand.
  • the water pressure is reduced to 2-6 bar by reducing the pipe diameter and shortening the pipe resistance.
  • the granular melt is cooled again, and the outer surface strength continues to rise but the pressure difference becomes large and then expands again.
  • the expansion rate is lowered to a very low level.
  • the pipe diameter and length are adjusted to reduce the pipe resistance to reduce the water pressure to 1-4 bar.
  • the granular melt continues to cool, and the outer surface strength further rises but the pressure difference is still increasing. It will also swell but because the cooling time is sufficient for the outer skin of the granules to be very strong and the particles are also substantially crystallized to stabilize the outer diameter of the granules.
  • the granulated and expanded polymer enters the centrifugal separator together with water, where the water and the expanded particles are separated, and the expanded particles enter the vibrating screen and enter the post-treatment system, and the process water flows out of the centrifugal separator into the process water tank. This is repeated so that the process continues.
  • a multi-stage pressure-releasing expansion process water line whose pressure is gradually reduced, in order to provide a suitable, controllable and stable pressure-expanding environment for the pellets entering the underwater pelletizing chamber from the die, and thus further It is beneficial to the foaming molding of the subsequent pelletizing structure, and can ensure the controllable and stable rate of foaming and puffing, avoiding the breakage of the particle cells in the conventional pressure-expanding environment, the foaming collapse cannot be formed, or the expansion ratio is uncontrollable. problem.
  • High molecular weight polymers and low molecular weight polymers, high hardness polymers and low hardness polymers, high crystalline polymers and low crystalline to amorphous polymers, highly polar polymers and low or non-polar are distinguished by comparing two polymer materials (preferably the same or similar polymer materials) having different physical properties, that is, two polymer materials of different physical properties, molecular weight. Higher is defined as a high molecular weight polymer, and a lower molecular weight is defined as a low molecular weight polymer.
  • high hardness and low hardness are also analogously defined. More preferably, the molecular weight of the high molecular weight polymer is at least twice as high as that of the low molecular weight polymer; the hardness of the high hardness polymer should be more than 10 A worse than the low hardness polymer.
  • the pressure-resisting resilient polymer material mainly used for rebounding should be selected from elastomer-based polymer materials, such as TPU, rubber, TPE, etc., and the support skeleton polymer material which mainly serves as a support may be an elastomer-like polymerization. Materials, non-elastomeric materials such as PET, PTT, etc. can also be selected.
  • thermoplastic polyurethanes can be prepared directly using commercially available products or according to known process techniques. More preferably, the thermoplastic polyurethane may be selected such as a polyether thermoplastic polyurethane or a polyester thermoplastic polyurethane depending on the product requirements.
  • the size, size and density of the internal micro-balloons of the expanded particles, as well as the form, size and density of the interior and skin open cells of the expanded particles are designed and controlled by optimizing the raw material selection and ratio, and at the same time, through the heat
  • the pressure of the molten polymer melt in the screw of the twin-screw extruder and the pressure of the extruder to control the expansion of the bubble core and finally, by the method of the difference between the melt pressure and the process water pressure and the process water release pressure
  • the body is solidified and shaped.
  • the present invention designs high molecular weight polymers and low molecular weight polymers, high hardness polymers and low hardness polymers, high crystalline polymers and low crystalline to amorphous polymers, highly polar polymers and low grades or
  • the non-polar polymers are separately combined, and then blended with hot melt to add a foaming agent, followed by a foaming agent in a different physical polymer raw material under a puffing process (preferably a controlled expansion process designed by the present invention)
  • a foaming agent in a different physical polymer raw material under a puffing process (preferably a controlled expansion process designed by the present invention)
  • the difference is that under the same operating conditions, the polymer raw material supported by the skeleton is fast in forming and weak in foaming ability, and the foaming agent has a short foaming time in the interior thereof, and generally only emits a closed cell structure of the extremely closed airbag, forming
  • the skeleton is supported, and the polymer raw material which is a low-pressure-resistance material has
  • a number of tiny closed airbags of 0.01 to 20 micrometers formed by a high molecular weight or high hardness or high crystalline or highly polar polymer material and a foaming agent under the action of a nucleating agent are used in the expanded material.
  • Used as a support component and low molecular or low hardness or low crystal or low polarity / non-polar polymer forms very fine open cells (non-closed pores) with the foaming agent, and combined with partial expansion to become a low pressure withstand
  • the projectile assembly in the open cells, forms an air passage around the expanded material in the expanded material, and the air passages partially communicate with each other and extend to the surface of the expanded material particles.
  • the micro-closed air bag hole in the support assembly is squeezed to support the effect, and the air in the open cell in the slow-resistance rebound assembly is quickly squeezed out to give the puffed material.
  • the present invention can also utilize the difference in permeability of different blowing agents in different polymer materials during the preparation process, the difference in melt strength between different materials in different pressure differences and the crystallization rate of the melt, different polymerizations.
  • the difference in physical properties and physical property retention after puffing thereby controlling the size and number of micro-balloons in the puffed material, as well as the size, shape and shape of the open cells to adjust the physical properties of the material to meet the requirements of different downstream uses and customer requirements.
  • the inlet pressure of the melt boosting pump is increased at a constant process water temperature, thereby indirectly increasing the inlet pressure of the die and passing the process water. Pressure accelerates pressure release.
  • the inlet pressure of the melt boosting pump is reduced at a constant process water temperature, the inlet pressure of the die is indirectly reduced, and the pressure is relieved by the process water pressure.
  • the present invention has the following advantages:
  • the present invention adopts a polymer raw material of different physical properties to form a suitable micro-balloon structure during expansion and foaming.
  • Moderate open cells form a entangled network air passage interpenetrating structure, so that the micro-balloon structure can provide good physical properties such as strength, elastic modulus and resilience, while the open cell structure can improve the material.
  • Energy absorption, energy storage, contact and comfort. The entire material as a whole provides better cushioning feedback.
  • the adjustment of the formula and the adjustment of the process conditions can effectively adjust the structure, opening form, density, size, etc. of the micro-airbags and open cells, and can effectively control the volume of the micro-balloons in the material by about 20 to 99.5%.
  • the open cells account for about 0.5 to 80% of the volume of the material.
  • the back pressure of the hot melt in the twin-screw extruder and the back pressure of the underwater pelletizing chamber can be controlled to stabilize the speed and rate of the pressure expansion and puff, thereby achieving precise control of the material expansion ratio.
  • the multi-stage step-by-step pressure release process can flexibly control the requirements of the bubble breaking rate in the expansion process of different polymers to achieve the production of suitable composite expanded structural materials.
  • the particle size of the controlled expanded particles is 0.6 to 25 mm by controlling the inlet pressure of the melt pump and the opening size of the orifice plate.
  • the polymer elastomer material prepared by the invention is suitable for application fields of foam materials such as shoe products, packaging, shock absorption, heat preservation, seats, runways, solid tires and the like.
  • Figure 1 is a process flow diagram of the present invention
  • compositions, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not specifically listed or inherent to such compositions, steps, methods, articles or devices. Elements.
  • Approximating terms used in the specification and claims are used to modify the quantity, and the invention is not limited to the specific number, and includes a portion that is close to the quantity that is acceptable without causing a change in the relevant basic function.
  • a numerical value is modified by "about”, “about” or the like, meaning that the invention is not limited to the precise value. In some instances, the approximation may correspond to the accuracy of the instrument that measures the value.
  • the scope of the invention may be combined and/or interchanged, and if not stated otherwise, the scope includes all subranges.
  • Polymer means a polymeric compound prepared by polymerizing monomers of the same or different types.
  • the generic term “polymer” encompasses the terms “homopolymer,” “copolymer,” “terpolymer,” and “interpolymer.”
  • thermoplastic micro-balloon polymer elastomer material comprising the following components by weight percentage: 0.1-97% of the support skeleton polymer material, 0.1-97% of the pressure-resistant slow rebound polymer material, and a nucleating agent 0.01 to 0.5%, and the foaming agent is 0.1 to 10%.
  • the support skeleton polymer material is a high molecular weight, high hardness, high crystalline or high polarity polymer material
  • the pressure resistant slow rebound polymer material is a support matrix polymer.
  • the material corresponds to a low molecular weight, low hardness, low crystallization to amorphous, low polarity/non-polar polymer material.
  • the support skeleton polymer material is a high molecular weight polyurethane
  • the corresponding pressure-resistant slow rebound polymer material is a low molecular weight polyurethane
  • the support skeleton polymer material is a high-hardness thermoplastic polymer elastomer (which may be selected according to actual conditions such as TPU, TPE or rubber, etc.), and the corresponding pressure-resistant slow-rebound polymer material is low-hardness thermoplastic polymer elasticity. body;
  • the support skeleton polymer material is polyamide or polyester, and the corresponding pressure-resistant slow rebound polymer material is thermoplastic polyurethane.
  • the high molecular weight polyurethane has a molecular weight Mw of from 8 ⁇ 10 4 to 5 ⁇ 10 5 and a molecular weight M w of the low molecular weight polyurethane of from 2 ⁇ 10 4 to 2.5 ⁇ 10 5 . ;
  • the high hardness thermoplastic polymer elastomer has a Shore hardness of 80A to 75D, and the low hardness thermoplastic polymer elastomer has a Shore hardness of 30 to 85A;
  • the polyester or polyamide is a modified low melting point polyester or a modified low melting point polyamide, respectively, and controls the difference in melting point between the support skeleton polymer material and the pressure resistant rebound polymer material at 20 °C.
  • the modified low melting point polyester may be selected such as modified PET, PTT, PBT, etc.
  • the modified low melting point polyamide may be modified as low melting point PA6, PA6I, PA11, PA12, PA9 and the like.
  • the nucleating agent is selected from at least one of carbon nanotubes, silica, talc, modified calcium carbonate, carbon black or tetrafluoroethylene powder;
  • the blowing agent is at least one selected from the group consisting of CO 2 , N 2 , n-butane, n-pentane or isopentane.
  • the polymeric elastomer material has a particle size of from 0.6 to 25 mm.
  • the invention also proposes a preparation method of the above thermoplastic micro-balloon polymer elastomer material, comprising the following steps:
  • the temperature of the twin-screw extruder in step (1) is 160-300 ° C, and the length-to-diameter ratio of the twin-screw extruder is 32-56;
  • the temperature in the static mixer is set to 120-280 ° C, and the inlet pressure of the melt pump is such that the difference between the hot melt pressure extruded through the die and the pressure of the process water in the underwater pelletizing chamber is 70-120 bar.
  • the process water temperature in the underwater pelletizing chamber in step (2) is 10-90 ° C, the pressure is 4-15 bar;
  • the multi-stage pressure-releasing expansion process water pipeline is gradually reduced by pressure.
  • the multi-stage pressure release expansion process water line in the step (2) is a four-stage process water line, wherein the first stage process water line has a water pressure of 4-15 bar, and the second stage process The water pressure of the water line is 3-10 bar, the water pressure of the third stage process water line is 2-6 bar, and the water pressure of the fourth stage process water line is 1-4 bar.
  • the twin-screw extruder 2 is driven by the motor 1 at a speed of 50-900 rpm, and the screw setting temperature of the twin-screw extruder 2 is 160-300. °C ensures that the thermoplastic polymer is sufficiently hot melted, the polymer feedstock and nucleating agent are fed from the feed port 3 at the front end, and the blowing agent is fed from the feed port 2 of the middle section.
  • each raw material After mixing, under heating and shearing force of the screw, each raw material is hot melted and after the screw is fully mixed, it enters the static mixer 5, and the melt is further homogenized and cooled in the static mixer 5 to ensure the melt temperature is Between 120 and 280 ° C, the specific can be controlled according to the physical properties of the finished product.
  • the inlet pressure of the melt pump 6 is set to be between 50 and 200 bar, and the melt pressure in the screw of the twin-screw extruder 2 is controlled to be stable.
  • the mixed foaming agent and the nucleating agent are thoroughly mixed and homogenized in a hot melt in a controlled high pressure environment.
  • the high pressure hot melt is stably pushed into the die 7 of the extruder by the pressure control and quantitative transfer function of the melt pump 6, and the die 7 is a porous orifice plate structure, and the inside thereof is uniformly heated to ensure the stability of the hot melt. Pass the die 7.
  • the hot melt sent out by the high pressure of the melt pump 6 is cut into the granules of the beans by the dicing knife which is rotated by the high speed in the underwater dicing chamber 8 through the respective holes of the die 7, and the dicing knife of the underwater dicing chamber 8 is actually in the water.
  • the hot melt is cut down.
  • the process water of 10 to 90 ° C generates a pressure of 4 to 15 bar under the action of the process water pump assembly 16 (including a water pump and a water tank, etc.), and enters the underwater pelletizing chamber 8 through the process water inlet pipe 9.
  • the high pressure hot melt thus extruded from the die 7 is rapidly cooled under high pressure process water and cut into pellets by a pelletizing knife. Since there is a pressure difference between the high pressure hot melt and the high pressure process water, and the pressure difference can be adjusted by the inlet pressure of the melt pump 6 and the delivery pressure of the process water pump assembly 16, the polymerization is cut into pellets throughout the process.
  • the initial expansion rate and rate of the material are controllable and stable.
  • a multi-stage pressure-release expansion process water line (here preferably four stages) is specially designed in the process, and the granular polymerization is utilized.
  • the water pressure of 4-15 bar is maintained in the first-stage process water line (ie, the process water primary pressure release pipe 10).
  • the granular melt partially cools and preliminarily expands in the presence of a pressure difference.
  • the water pressure is reduced to 3 to 10 bar by the diameter of the pipeline becoming shorter and shorter, and the granular melt is further cooled, and the outer surface strength is increased but the pressure difference is When it becomes bigger, it will expand again.
  • the third-stage process water line ie, the process water third-stage pressure release pipe 12
  • the water pressure is reduced to 2-6 bar by reducing the pipe diameter and shortening the pipe resistance. At this time, the granular melt is cooled again, and the outer surface strength is It continues to rise but the pressure difference becomes larger and then expands again. However, since the crystallization of the particles is almost completed, the expansion rate is lowered to a very low level.
  • the pipe diameter and length adjustment are used to reduce the pipe resistance to reduce the water pressure to 1-4 bar, at which time the granular melt continues to cool, and the outer surface strength Further rise, but the pressure difference will still expand after it becomes larger, but because the cooling time is sufficient, the outer skin strength of the particles is already high and the particles are also substantially crystallized to stabilize the outer diameter of the particles.
  • the granulated and expanded polymer enters the centrifugal separator 14 together with water, where the water and the expanded product are separated, and the expanded particles enter the vibrating screen 15 and enter the post-treatment system to produce a puffed product output, and the process water is centrifuged.
  • the separator 14 flows out into the process water pump assembly 16. This is repeated so that the process continues.
  • the above preparation method is only a preferred process for preparing the cell structure in which the above-mentioned open-hole and closed-cell structures are combined, except for the above-mentioned preferred process for continuous foaming by screw.
  • the present invention is also prepared by a conventional foaming process such as a kettle foaming method on the basis of the foaming formulation which can be foamed out of a plurality of cell structures, which is also provided, and finally the obtained product can also be provided.
  • the polyether thermoplastic polyurethane used is from Bayer, Huntsman, etc.
  • the polyester thermoplastic polyurethane used is from Bayer, Huntsman, etc.
  • the low melting point polyester PET is derived from Jinshan Petrochemical, etc.
  • the modified low melting point polyamide used is from DuPont, Evonik and other companies
  • the PBT used is from Jinshan Petrochemical Company.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the polyether thermoplastic polyurethane having a molecular weight M w of from 150 K to 300 K (where K represents a unit of one thousand) is added to a polyether thermoplastic polyurethane having a ratio of 75% by weight (the same hereinafter) and a molecular weight M w of from 50 K to 100 K.
  • the addition ratio was 20%
  • the blowing agent was CO 2
  • the addition amount was 4.5%
  • the nucleating agent was calcium carbonate
  • Twin screw extruder length to diameter ratio L / D 40, screw heating temperature 160-220 ° C, static mixer temperature 140-180 ° C, melt pump inlet pressure 100-120 bar, process water pressure 1228 or so, control pressure Poor (ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber) is 90-120 bar.
  • control pressure Poor ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • control pressure Poor ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • control pressure Poor ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • control pressure Poor ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • the water pressure in the first-stage process water line is controlled to be about 12 bar
  • thermoplastic microsphere polymer elastomer material prepared at the vibrating screen has a particle size of about 1-3 mm, and the volume of the formed microsphere structure is about 60-80%, and the open cells are opened. The volumetric proportion of the structure is about 10-35%.
  • FIG. 2-4 are SEM photographs of different dimensions of the microsphere polymer elastomer material prepared in the above Example 1, and it can be seen from the figure that the microparticle structure and opening can be clearly seen in the material particles.
  • FIG. 5-8 is the SEM photograph of the different scales of the surface of the micro-balloon polymer elastomer material of the above Embodiment 1, as can be seen from the figure, the air passage has been extended To the surface of the material particles.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the polyether thermoplastic polyurethane having a molecular weight M w of from 300 K to 500 K (where K represents a unit of one thousand) is added to a polyether thermoplastic polyurethane having a ratio of 60% by weight (the same applies hereinafter) and a molecular weight M w of from 150 K to 250 K.
  • the addition ratio was 35%
  • the blowing agent was N 2
  • the addition amount was 4.95%
  • the nucleating agent was carbon black
  • the amount added was 0.05%.
  • Twin screw extruder length to diameter ratio L / D 56, screw heating temperature 160-220 ° C, static mixer temperature 140-180 ° C, melt pump inlet pressure 100-150 bar, process water pressure 6 bar or so, control pressure
  • the difference ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • the water pressure in the first stage process water line is controlled to about 6 bar
  • the water pressure in the second stage process water line is controlled to about 5 bar
  • the water pressure in the third stage process water line is It is about 3 bar
  • the water pressure in the fourth-stage process water line is about 1 bar.
  • thermoplastic microsphere polymer elastomer material prepared at the vibrating screen has a particle size of about 8-12 mm, and the volume of the formed microsphere structure is about 30-50%, and the open cells are opened. The volumetric proportion of the structure is about 40-60%.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the polyether thermoplastic polyurethane having a molecular weight M w of 80K to 120K (where K represents a unit of one thousand) is added to a polyether thermoplastic polyurethane having a ratio of 97% by weight, the same molecular weight Mw of 20K to 50K,
  • the addition ratio is 0.1%
  • the blowing agent is N 2
  • the addition amount is 2.4%.
  • the nucleating agent is a mixture of talc powder and modified calcium carbonate in a mass ratio of 1:1, and the addition amount is 0.5%.
  • Twin-screw extruder length-to-diameter ratio L/D 46, screw heating temperature 160-220 °C, static mixer temperature 130-170 °C, melt pump inlet pressure 120-180 bar, process water pressure 15 bar or so, controlled release pressure
  • the difference i.e., the pressure difference between the high pressure hot melt at the outlet of the die and the process water in the underwater pelletizing chamber is 120-150 bar.
  • the water pressure in the first-stage process water line is controlled to be about 15 bar
  • the water pressure in the second-stage process water line is controlled to be about 10 bar
  • the water pressure in the third-stage process water line is It is about 6 bar
  • the water pressure in the fourth-stage process water line is controlled to about 4 bar.
  • thermoplastic microsphere polymer elastomer material prepared at the vibrating screen has a particle size of about 0.6-2 mm, and the volume of the formed microsphere structure is about 30-45%, and the open cells are opened.
  • the volume fraction of the structure is about 0.5-10%.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the polyether thermoplastic polyurethane having a molecular weight M w of 300K to 500K (where K represents a unit of one thousand) is added to a polyether thermoplastic polyurethane having a ratio of 0.1% by weight, the same molecular weight Mw of 20K to 50K, The addition ratio was 97%, the blowing agent was N 2 , the addition amount was 2.8%, and the nucleating agent was carbon nanotubes, and the amount added was 0.1%.
  • Twin screw extruder length to diameter ratio L / D 48, screw heating temperature 160-220 ° C, static mixer temperature 130-180 ° C, melt pump inlet pressure 90-120 bar, process water pressure 10 bar or so, control pressure
  • the difference ie, the pressure difference between the high pressure hot melt at the outlet of the die and the process water in the underwater pelletizing chamber
  • the water pressure in the first-stage process water pipeline is controlled to be about 10 bar
  • the water pressure in the second-stage process water pipeline is controlled to be about 7 bar
  • the water pressure in the third-stage process water pipeline is It is about 4 bar
  • the water pressure in the fourth-stage process water line is controlled to be about 2 bar.
  • thermoplastic microsphere polymer elastomer material prepared at the vibrating screen has a particle size of about 12-25 mm, and the volume of the formed microsphere structure is about 20%, and the open cell structure is The volume ratio is about 60-70%.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the polyether thermoplastic polyurethane having a molecular weight M w of from 120K to 180K (where K represents a unit of one thousand) is added to a polyether thermoplastic polyurethane having a ratio of 70% by weight, the same molecular weight Mw of 20K to 50K, The ratio of addition is 19.7%, the foaming agent is CO 2 and N 2 added in a volume ratio of 1:1, and the amount of addition is 10%.
  • the nucleating agent is a mixture of calcium carbonate and tetrafluoroethylene powder in a mass ratio of 1:1. 0.3%.
  • Twin-screw extruder length-to-diameter ratio L/D 40, screw heating temperature 180-240 °C, static mixer temperature 140-190 °C, melt pump inlet pressure 100-120 bar, process water pressure 10 bar or so, controlled release pressure Poor (ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber) is 90-120 bar.
  • controlled release pressure Poor ie, the pressure difference between the high pressure hot melt at the exit of the die and the process water in the underwater pelletizing chamber
  • the water pressure in the first-stage process water pipeline is controlled to be about 10 bar
  • the water pressure in the second-stage process water pipeline is controlled to be about 7 bar
  • the water pressure in the third-stage process water pipeline is It is about 4 bar
  • the water pressure in the fourth-stage process water line is controlled to be about 2 bar.
  • thermoplastic microsphere polymer elastomer material prepared at the vibrating screen has a particle size of about 3-6 mm, and the volume of the formed microsphere structure is about 60%, and the open cell structure is The volume ratio is about 10%.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 70-80%, and the volume of the open cell structure is about 15-30%.
  • the polyester type thermoplastic polyurethane with Shore A hardness of 80A is added in an amount of 80% (weight percent, the same below), the polyester type thermoplastic polyurethane having a Shore hardness of 30A is added in an amount of 19.5%, and the blowing agent is selected from CO 2 and N 2 .
  • the mixture with a weight ratio of 1:1 was added in an amount of 0.4%, and the nucleating agent was selected from a mixture of carbon nanotubes, talc and calcium carbonate in a total amount of 0.1%.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 70-80%, and the volume of the open cell structure is about 15-30%.
  • the polyester-type thermoplastic polyurethane with a Shore hardness of 75D is added in an amount of 70% (weight percent, the same below), the polyester-type thermoplastic polyurethane having a Shore hardness of 85A is added in an amount of 27.5%, and the blowing agent is selected from CO 2 and N 2 .
  • the mixing ratio of 1:1 by weight is 2%, and the nucleating agent is a mixture of carbon nanotubes, talc and calcium carbonate, and the total amount is 0.5%.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 60-70%, and the volume of the open cell structure is about 25-40%.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 70-80%, and the volume of the open cell structure is about 15-30%.
  • thermoplastic micro-balloon polymer elastomer material of the present invention is prepared according to the following process recipe of Figure 1 according to the following raw material formulations and process conditions:
  • the modified low-melting polyester PET is added in a proportion of 60% (weight percent, the same below), and the polyester polyurethane is added in a ratio of 37% (the melting point difference between the modified low-melting polyester PET and the polyester polyurethane is 20 ° C),
  • the nucleating agent was carbon black in an amount of 0.5%
  • the blowing agent was a mixture of CO2 and N2, which was added in an amount of 2.5%.
  • Twin-screw extruder long-distance ratio L/D 52, screw heating temperature 220-280°C, static mixer temperature 160-200°C, melt pump inlet pressure 100-150bar, process water pressure 15bar or so, controlled release pressure
  • the difference i.e., the pressure difference between the high pressure hot melt at the outlet of the die and the process water in the underwater pelletizing chamber
  • the water pressure in the first-stage process water pipeline is controlled to be about 15 bar
  • the water pressure in the second-stage process water pipeline is controlled to be about 12 bar
  • the water pressure in the third-stage process water pipeline is It is about 8 bar
  • the water pressure in the fourth-stage process water line is about 4 bar.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 50-80%, and the volume of the open cell structure is about 5-50%.
  • Example 10 Compared with Example 10, the same was true except that the modified low melting point polyester PET was replaced with a modified low melting point polyamide (PA).
  • PA modified low melting point polyamide
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 50-80%, and the volume of the open cell structure is about 5-50%.
  • Example 10 Compared with Example 10, the same was true except that the modified low melting point polyester PET was replaced with PBT.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined.
  • a micro-balloon structure closed cell structure
  • an open-cell structure Referring to the cell structure shown in FIGS. 2-8, In the material, the volume of the formed micro-balloon structure is about 50-80%, and the volume of the open cell structure is about 5-50%.
  • Example 2 Compared with Example 1, except that the blowing agent was changed to n-butane, n-pentane or isopentane, respectively, the others were the same.
  • thermoplastic micro-pore polymer elastomer material prepared in the above embodiment 13 to the fibril sieve also has a cell structure in which a micro-balloon structure (closed cell structure) and an open-cell structure are combined, and referring to FIG. 2 to FIG. The cell structure shown.
  • the pellets are directly subjected to a process temperature of 40-50 ° C, a pressure of 4-8 bar, and a substantially stable temperature and pressure. The rest are the same.
  • thermoplastic micro-balloon polymer elastomer material prepared at the vibrating screen also has a cell structure in which the micro-balloon structure (closed cell structure) is combined with the open-cell structure, and the cell structure shown in FIGS. 2 to 8 is referred to.
  • the foamed particles of this example partially had cell breakdown phenomenon.
  • the foaming temperature is about 150 ° C and the pressure is about 15 MPa.
  • the prepared foamed particles may also have a cell structure which is combined with the micropore structure (closed cell structure) of the foamed particles in FIG. 1-8 and the open cell structure, but the cell structure is not stable and is easy to shrink. .
  • polyether thermoplastic polyurethane in the present embodiment is entirely made of 150K to 300K polyether thermoplastic polyurethane, the others are the same.
  • Example 7 Compared with Example 7, except that the polymer raw materials in this example were all made of a polyester thermoplastic polyurethane having a Shore hardness of 80 A, the same was true.
  • Example 10 Compared with Example 10, except that the polymer raw materials in this example were all made of the same modified low melting point polyester PET (i.e., without the addition of polyester type polyurethane), the others were the same.
  • the foamed materials prepared in the three comparative examples of Comparative Example 1 to Comparative Example 3 were examined and analyzed for the cell structure.
  • the skins of the foamed particles obtained in the above three comparative examples were continuous epidermis, and The inside of the particle incision scan can be found to be substantially all closed-cell structure, and there is no open-cell structure extending to the epidermis as shown in FIG. 5 to FIG. 8 of the embodiment 1, and the expansion ratio is compared with the two polymer materials. For mixed formulations, it is significantly lower.
  • the present invention improves the formulation of the foamed granules by using a single closed polymer foamed granule product prepared by using a single physical polymer as a raw material. Two kinds of polymers with different physical properties are used as raw materials, and combined with the difference in foaming ability of the foaming agent in the two polymers during the foaming process, foamed particles having a cell structure in which open cells and closed cells are combined are prepared.

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Abstract

本发明涉及一种热塑性微气囊聚合物弹性体材料及其制备，热塑性微气囊聚合物弹性体材料的配方包括以下重量百分比含量的组分：支撑骨架聚合物材料0.1-97％，耐压慢回弹聚合物材料0.1-97％，成核剂0.01～0.5％，发泡剂0.1～10％；所述的支撑骨架聚合物材料为高分子量、高硬度、高结晶或高极性聚合物材料，所述的耐压慢回弹聚合物材料为与支撑骨架聚合物材料相对应的低分子量、低硬度、低结晶至无定形态、低极性/无极性聚合物材料。与现有技术相比，本发明制备的聚合物弹性体材料中由微气囊结构与开口泡孔形成缠绕网络起到互穿结构，回弹力等材料物性优异，缓冲回馈利落，接触感与舒适性高，膨化倍率可控等。

Description

热塑性微气囊聚合物弹性体材料及其制备 技术领域
本发明涉及高分子材料制备领域，尤其是涉及一种热塑性微气囊聚合物弹性体材料及其制备。
背景技术
热塑性聚合物弹性材料广泛制造生产和生活所用设施，设备，工具和消耗品，随着社会的发展对环保，节能，降耗等方面的要求，材料轻量化的需求也变得越来越紧迫。热塑性聚合物弹性材料也大量开始轻量化的实验和验证并持续推广应用。例如，聚丙烯PP发泡、聚乙烯PE发泡、聚苯乙烯PS发泡、聚酯PET发泡、聚酰胺PA发泡和聚氨酯TPU发泡等。
目前热塑性聚合物弹性体的膨化常见的工艺路线有：浇注模内膨化发泡、注塑膨化发泡、挤塑膨化发泡、高压釜内膨化发泡等。注塑发泡的发泡均匀性和发泡倍率较差，挤塑发泡的材料易熔体破裂导致泡孔击穿和表面塌陷，高压釜内发泡存在较高安全风险和产能效率低。按发泡原理分为：物理发泡和化学发泡。不论选取哪一种聚合物原料，也不论采用哪一种发泡方法，其发泡过程一般都要经过：形成气泡核→气泡核膨胀→泡体固化定型等阶段。
热塑性聚合物弹性材料的发泡和膨化后仍然需保有良好的物性，这就要求对膨化后材料结构和材料泡孔等进行设计。但受制于材料本身结构性质以及加工工艺、发泡原理的理解等诸多方面，现有的发泡颗粒等制品一般都是采用单一聚合物原料与发泡剂在膨化工艺下制备，这样制备得到的具有稳定结构不坍塌的发泡颗粒基本均为连续表皮的纯闭孔结构，这种泡孔结构的发泡颗粒虽然具有较高的支撑强度，但是由于其表皮连续，受压时内部气体无法排出，导致发泡颗粒手感偏硬，且这种闭孔式的泡孔结构颗粒在受压时基本难以实现正向反馈，因此，当用在鞋材制品上时容易发生侧滑现象。此外，国内外对膨化的热塑性聚合物弹性材料的控制方式简单和不稳定，使得特别是如尼龙、PET、PPT、热塑性聚氨酯等在材料性质、加工工艺上鲜有稳定可控膨化案例。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种热塑性微气囊聚合物弹性体材料及其制备方法。
本发明的目的可以通过以下技术方案来实现：
本发明的目的之一在于提出了一种热塑性微气囊聚合物弹性体材料，包括以下重量百分比含量的组分：支撑骨架聚合物材料0.1-97％，耐压慢回弹聚合物材料0.1-97％，成核剂0.01～0.5％，发泡剂0.1～10％。
作为优选的实施方案，所述的支撑骨架聚合物材料为高分子量、高硬度、高结晶或高极性聚合物材料，所述的耐压慢回弹聚合物材料为与支撑骨架聚合物材料相对应的低分子量、低硬度、低结晶至无定形态、低极性至无极性聚合物材料。
作为上述优选的实施方案的更优选，所述的支撑骨架聚合物材料为高分子量聚氨酯，其对应的耐压慢回弹聚合物材料为低分子量聚氨酯；
或所述的支撑骨架聚合物材料为高硬度热塑性聚合物弹性体(可以根据实际情况选择如TPU、TPE或橡胶等)，其对应的耐压慢回弹聚合物材料为低硬度热塑性聚合物弹性体；
或所述的支撑骨架聚合物材料为聚酰胺或聚酯，其对应的耐压慢回弹聚合物材料为热塑性聚氨酯。
作为上述更优选的实施方案的更进一步优选，所述的高分子量聚氨酯的分子量M w为8×10 4～5×10 5，低分子量聚氨酯的分子量M w为2×10 4～2.5×10 5。
作为上述更优选的实施方案的更进一步优选，高硬度热塑性聚合物弹性体的邵氏硬度为80A～75D，低硬度热塑性聚合物弹性体的邵氏硬度为30～85A，此时，高硬度与低硬度两种热塑性聚合物弹性体一般选用同类物质。
作为上述更优选的实施方案的更进一步优选，聚酯或聚酰胺分别为改性低熔点聚酯或改性低熔点聚酰胺，并控制支撑骨架聚合物材料和耐压回弹聚合物材料的熔点差在20℃内。更优选的，改性低熔点聚酯可以选择如改性PET、PTT、PBT等，改性低熔点聚酰胺可以如低熔点改性的PA6、PA6I、PA11、PA12、PA9等。(选择低熔点的改性聚酰胺或改性聚酯的主要原因是因为一般的聚酯或聚酰胺的熔点比聚氨酯高很多，这样就导致两者在作为原料制备发泡制品时，很难调节合适的加工温度，进而导致很容易发生部分原料组分发生过熔融或混合不充分等问题)
作为优选的实施方案，所述的成核剂选自碳纳米管、二氧化硅、滑石粉、改性碳酸钙、炭黑或四氟乙烯粉剂中的至少一种；
所述的发泡剂选自CO 2、N 2、正丁烷、正戊烷或异戊烷中的至少一种。
作为优选的实施方案，所述的聚合物弹性体材料的粒径为0.6-25mm。
本发明的热塑性微气囊聚合物弹性体材料可以在上述基础配方的基础上，根据要制得的材料性能的需求选择性加入入光稳定剂、抗氧剂等其他功能性助剂。
上述目的之一的热塑性微气囊聚合物弹性体材料可以在其配方基础上通过常规的发泡工艺(如釜式发泡等)制备得到，本发明目的之二还在于在常规发泡工艺外，另提出了一种上述热塑性微气囊聚合物弹性体材料的新制备方法，包括以下步骤：
(1)将支撑骨架聚合物材料、耐压慢回弹聚合物材料和成核剂从双螺杆挤塑机前端加料口喂入，发泡剂从双螺杆挤塑机中段加料口喂入，使各原料热熔混合充分后，再进入静态混合器进一步均质化，接着再经熔体泵控压和定量输送；
(2)被熔体泵送出的热熔体通过模头进入水下切粒室切粒，并由工艺水带出分离，所得颗粒筛选干燥后即形成目的产品。
作为优选的实施方案，步骤(1)中双螺杆挤塑机的温度为160～300℃，双螺杆挤出机长径比为32-56；
静态混合器内的温度设定为120-280℃，熔体泵的入口压力为50-200bar，并控制经模头挤出的热熔体压力与水下切粒室中工艺水的压力之差为70-120bar。
作为优选的实施方案，步骤(2)中水下切粒室中的工艺水温度为10-90℃，压力为4-15bar；
切粒被工艺水带出时，经过各级压力逐级降低的多级释压膨胀工艺水管线输送。
作为上述优选的实施方案的进一步优选，步骤(2)中多级释压膨胀工艺水管线为四级工艺水管线，其中，第一级工艺水管线的水压力保持与进入水下切粒室的工艺水压力一致。更优选的，第一级工艺水管线的水压为4-15bar，第二级工艺水管线的水压为3-10bar，第三级工艺水管线的水压为2-6bar，第四级工艺水管线的水压为1-4bar。
更为具体的制备方法中，双螺杆挤塑机在电机的驱动下使双螺杆挤塑机在50～900rpm转速运行，挤塑机的螺筒设定温度优选160～300℃确保热塑性聚合物能充分热熔，聚合物和成核剂从前端螺杆加料口喂入，发泡剂从中段的螺杆加料口喂入。混合后在挤塑机加热以及螺杆的剪切力下，各材料被热融并在螺杆混合充分后 进入静态混合器，熔体在静态混合器中进行深一步均质化和冷却确保熔体温度在120～280℃之间可依照成品物性要求可控。通过熔体泵的控压和定量输送作用，设定熔体泵的入口压力在50～200bar之间控制挤塑机螺膛内熔体压力稳定，使混合发泡剂和成核剂的热熔体中在可控的高压环境中充分混合和均化。通过熔体泵控压和定量输送功能将高压热熔体稳定的推入挤塑机模头，模头为多孔的孔板结构，其内部含均匀加热设施确保热熔体能稳定通过模头。被熔体泵高压送出的热熔体通过模头的各个孔在水下切粒室被高速旋转的切粒刀切成豆粒状颗粒，水下切粒室的切粒刀实际是在水下分切热熔体。优选10～90℃的工艺水在工艺水泵的作用下产生4～15bar的压力通过切粒水室的工艺水进水管进入水下切粒室，这样高压热熔体在高压工艺水下被快速冷却并被切粒刀切成粒状。由于高压热熔体与高压工艺水之间存在压差，而且这种压差可以通过熔体泵的进口压力和变频工艺水泵压力来调整，使得整个工艺中被切成粒状的聚合物初始膨胀速率和倍率可控和稳定。因为刚切下的粒状聚合物的冷却时间短和不同配方中材料结晶速度的差异很大，在本工艺中特别优选设计了多级释压膨胀工艺水管线，利用粒状聚合物的外表皮在工艺水中停留时间越长强度越高，承压条件越高的原理(停留时间的长短可以通过设置管线的长短来进行控制)，在第一级工艺水管线中仍然维持4～15bar的水压，此时粒状熔体部分冷却并在压差存在的条件下初步膨胀。在第二级工艺水管线中通过管线直径的变大和变短将水压降至3～10bar，此时粒状熔体进一步冷却外表面强度上升但压差变大后也会再膨胀。在第三级工艺水管线中通过管线直径的变大和变短降低管阻将水压降至2～6bar，此时粒状熔体再次冷却，外表面强度继续上升但压差变大后也再次膨胀但由于颗粒结晶快要完成所以膨胀速率降至很低。在第四级工艺水管线中还是通过管线直径和长度调整来降低管阻将水压降至1～4bar，此时粒状熔体继续冷却，外表面强度进一步上升但压差仍在变大后也还会膨胀但因为冷却时间足够颗粒外表皮强度已很高并且粒子也基本结晶完成使颗粒外径定型稳固。粒状膨化后的聚合物与水共同进入离心式分离机中，在这里水和膨化的粒子分离，膨胀后的粒子进入振动筛进入后处理系统，工艺水从离心式分离机中流出进入工艺水箱。如此反复，使工艺连续进行。本发明中优选采用压力逐级降低的多级释压膨胀工艺水管线的原因是为了给从模头被进入水下切粒室的切粒提供合适、可控、稳定的释压膨化环境，进而更加利于后续切粒结构的发泡成型，并可保证发泡膨化的倍率的可控和稳定，避免常规释压膨化环境中颗粒泡孔易击穿、发泡坍塌无法成型或发泡倍率不 可控等问题。
本发明中所涉及的高分子量聚合物与低分子量聚合物、高硬度聚合物与低硬度聚合物、高结晶聚合物与低结晶至无定形态聚合物、高极性聚合物与低级性或无极性聚合物等组合中的高分子量与低分子量等是由物性不同的两种聚合物材料(优选同种或同类聚合物材料)对比来进行区分的，即不同物性的两种聚合物原料，分子量较高的即定义为高分子量聚合物，分子量较低的则定义为低分子量聚合物，同理，高硬度和低硬度等也是类比定义的。更优选的，高分子量聚合物的分子量比低分子量聚合物至少大一倍以上；高硬度聚合物的硬度应比低硬度聚合物的差10A以上。
本发明中，主要起回弹作用的耐压回弹聚合物材料应选择弹性体类聚合物材料，如TPU、橡胶、TPE等，主要起支撑作用的支撑骨架聚合物材料可以为弹性体类聚合物材料，也可以选择非弹性体材料，如PET、PTT等。
本发明中若无特别说明，各原料以及涉及的工艺步骤可以采用任何本领域技术人员已知的原料或工艺技术。如热塑性聚氨酯可以直接采用市售产品或根据已知的工艺技术自己制备。更优选的，热塑性聚氨酯可以根据产品需要选择如聚醚型热塑性聚氨酯或聚酯型热塑性聚氨酯。
本发明在制备时，通过对原料选择与配比优化来设计和控制膨化颗粒的内部微气囊大小、尺寸、密度，以及膨化颗粒内部和表皮开泡孔的形式、尺寸和密度，同时，通过热熔融聚合物熔体在双螺杆挤塑机螺膛内的压力和出挤塑机的压力来控制气泡核膨胀，最后，通过熔体压力与工艺水压力差和工艺水缓释压力的方法来控制泡体固化定型。
本发明在原料上通过设计高分子量聚合物与低分子量聚合物、高硬度聚合物与低硬度聚合物、高结晶聚合物与低结晶至无定形态聚合物、高极性聚合物与低级性或无极性聚合物分别组合，然后共混热熔后加入发泡剂，接着在膨化工艺下(优选本发明设计的可控膨化工艺)，利用发泡剂在不同物性聚合物原料中的发泡能力的差别，使得在同样操作工艺条件下，作为骨架支撑的聚合物原料成型快、发泡能力弱，发泡剂在其内部发泡时间短，一般仅发出极微密闭气囊的闭孔结构，形成骨架支撑，而作为耐压慢回弹件的聚合物原料成型慢、发泡能力强，发泡剂在其内部发泡时间长，可发出开孔结构并形成耐压慢回弹件，骨架支撑与耐压慢回弹件两种不同结构在发泡颗粒中混合共同组成开孔与闭孔复合的缠绕网状互穿气道结构复合膨化材料。其中，通过高分子量或高硬度或高结晶或高极性聚合物材料与发泡剂在 成核剂的作用下形成的无数0.01～20微米的微小密闭气囊，并由这些微小密闭气囊在膨化材料中充当支撑组件，而低分子或低硬度或低结晶或低极性/无极性聚合物则与发泡剂形成极细微开口泡孔(非密闭孔)，并与部分膨化组合成为耐压慢回弹组件，这些开口泡孔中在膨化材料中形成缠绕密闭微气囊的气道，且气道之间部分连通并延伸至膨化材料颗粒表面。这样，当膨化材料受到挤压时，支撑组件中的微小密闭气囊孔受挤压起到支撑效果，耐压慢回弹组件中的开口泡孔中的空气则迅速被挤压出去，赋予膨化材料良好的挤压柔软感，以及更好的支撑稳定性；而当挤压力消失时，微小密闭气囊则支撑膨化材料复位，外界空气随之被吸入开口泡孔中。整个材料整体能获得更好的缓冲回馈。
此外，本发明在制备过程中还可以利用不同的发泡剂在不同的聚合物材料中的渗透率差异，不同材料在不同压差中和熔体结晶速度导致的熔体强度的差异，不同聚合物膨化后物性变化以及物性保留的差异，从而控制膨化后的材料中微气囊大小与多少，以及开口泡孔大小，形状和多少来调整材料的物性达到满足不同下游用途和客户要求的目的。
本发明在制备过程中，当需要得到大开孔或开孔泡孔比例不足时，在恒定工艺水温度下，增加熔体增压泵入口压力，从而间接增加模头入口压力，并通过工艺水压力加速释压。当需要缩小开孔或开孔泡孔比例时，在恒定工艺水温度下，减小熔体增压泵入口压力，间接减小模头入口压力，并通过工艺水压力减缓释压。
与现有技术相比，本发明具有以下优点：
(1)相比于一般的采用单物性聚合物原材料制成的密闭微孔的膨化材料，本发明采用不同物性的聚合物原材料，使其在膨化发泡过程中形成具有合适的微气囊结构和适度的开口泡孔形成缠绕网络气道互穿结构，这样，微气囊结构可以为材料提供很好的物理性能，如强度、弹性模量和回弹力等，而开口泡孔结构则可以提高材料的吸能储能性、接触感和舒适感。整个材料整体能提供更好的缓冲回馈。
(2)通过对配方的调整和工艺条件调整可以有效调节微气囊和开口泡孔的结构、开口形式以及密度、大小等，并可有效控制材料中的微气囊占体积的20～99.5％左右，开口泡孔占材料体积的0.5～80％左右。
(3)本发明的制备过程中可以通过控制双螺杆挤塑机中的热熔体的背压和水下切粒室的背压来稳定释压膨化的速度和倍率，达到精准控制材料膨胀倍率的要求。
(4)采用多级逐步释压的过程，可以灵活控制不同聚合物膨胀过程中破泡率的要求从而达到制造合适的复合膨化结构材料。
(5)采用控制熔体泵入口压力和孔板的开孔大小等方式达到控制膨化颗粒粒径在0.6～25mm。
(6)本发明所制备的聚合物弹性体材料适用于鞋制品、包装、减震、保温、座椅、跑道、实心轮胎等发泡材料应用领域。
附图说明
图1为本发明的工艺流程图；
图2-4为本发明制得的微气囊聚合物弹性体材料内部的不同尺度的SEM照片；
图5-8为本发明制得的微气囊聚合物弹性体材料表面的不同尺寸的SEM照片；
图中，1-电机，2-双螺杆挤塑机，3-喂料口一，4-喂料口二，5-静态混合器，6-熔体泵，7-模头，8-水下切粒室，9-工艺水进口管，10-工艺水一级释压管，11-工艺水二级释压管，12-工艺水三级释压管，13-工艺水四级释压管，14-离心式分离机，15-振动筛，16-工艺水泵组件。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
另外，如果没有其它说明，所用原料都是市售的。
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。
如本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要 素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。
“聚合物”意指通过聚合相同或不同类型的单体所制备的聚合化合物。通用术语“聚合物”包含术语“均聚物”、“共聚物”、“三元共聚物”与“共聚体”。
本发明提出了一种热塑性微气囊聚合物弹性体材料，包括以下重量百分比含量的组分：支撑骨架聚合物材料0.1-97％，耐压慢回弹聚合物材料0.1-97％，成核剂0.01～0.5％，发泡剂0.1～10％。
作为一种优选的实施方案，所述的支撑骨架聚合物材料为高分子量、高硬度、高结晶或高极性聚合物材料，所述的耐压慢回弹聚合物材料为与支撑骨架聚合物材料相对应的低分子量、低硬度、低结晶至无定形态、低极性/无极性聚合物材料。
作为上述优选的实施方案的更优选，所述的支撑骨架聚合物材料为高分子量聚氨酯，其对应的耐压慢回弹聚合物材料为低分子量聚氨酯；
或所述的支撑骨架聚合物材料为高硬度热塑性聚合物弹性体(可以根据实际情况选择如TPU、TPE或橡胶等)，其对应的耐压慢回弹聚合物材料为低硬度热塑性聚合物弹性体；
或所述的支撑骨架聚合物材料为聚酰胺或聚酯，其对应的耐压慢回弹聚合物材料为热塑性聚氨酯。
作为上述更优选的实施方案的更进一步优选，所述的高分子量聚氨酯的分子量M w为8×10 4～5×10 5，低分子量聚氨酯的分子量M w为2×10 4～2.5×10 5；
高硬度热塑性聚合物弹性体的邵氏硬度为80A～75D低硬度热塑性聚合物弹性体的邵氏硬度为30～85A；
聚酯或聚酰胺分别为改性低熔点聚酯或改性低熔点聚酰胺，并控制支撑骨架聚合物材料和耐压回弹聚合物材料的熔点差在20℃内。更优选的，改性低熔点聚酯可以选择如改性PET、PTT、PBT等，改性低熔点聚酰胺可以如低熔点改性的PA6、PA6I、PA11、PA12、PA9等。
作为优选的实施方案，所述的成核剂选自碳纳米管、二氧化硅、滑石粉、改性碳酸钙、炭黑或四氟乙烯粉剂中的至少一种；
所述的发泡剂选自CO 2、N 2、正丁烷、正戊烷或异戊烷中的至少一种。
作为优选的实施方案，所述的聚合物弹性体材料的粒径为0.6-25mm。
此外，需要指出的，上述公开的仅是本发明的一个基础配方，在本发明公开的基础配方的基础上，本领域技术人员可以根据实际需要往其中添加其余常规的助剂，如添加抗氧化剂和抗老化剂等提高产品的抗老化性能。
本发明还提出了一种上述热塑性微气囊聚合物弹性体材料的制备方法，包括以下步骤：
(1)将支撑骨架聚合物材料、耐压慢回弹聚合物材料和成核剂从双螺杆挤塑机前端加料口喂入，发泡剂从双螺杆挤塑机中段加料口喂入，使各原料热熔混合充分后，再进入静态混合器进一步均质化，接着再经熔体泵控压和定量输送；
(2)被熔体泵送出的热熔体通过模头进入水下切粒室切粒，并由工艺水带出分离，所得颗粒筛选干燥后即形成目的产品。
作为上述优选的实施方案，步骤(1)中双螺杆挤塑机的温度为160～300℃，双螺杆挤出机长径比为32-56；
静态混合器内的温度设定为120-280℃，熔体泵的入口压力满足：经模头挤出的热熔体压力与水下切粒室中工艺水的压力之差为70-120bar。
作为上述优选的实施方案，步骤(2)中水下切粒室中的工艺水温度为10-90℃，压力为4-15bar；
切粒被工艺水带出时，经过压力逐级降低的多级释压膨胀工艺水管线输送。
作为上述优选的实施方案的进一步优选，步骤(2)中多级释压膨胀工艺水管线为四级工艺水管线，其中，第一级工艺水管线的水压为4-15bar，第二级工艺水管线的水压为3-10bar，第三级工艺水管线的水压为2-6bar，第四级工艺水管线的水压为1-4bar。
进一步更优选的，上述制备过程的详细说明可见附图1，双螺杆挤塑机2在电机1的驱动下以50～900rpm转速运行，双螺杆挤塑机2的螺筒设定温度160～300℃确保热塑性聚合物能充分热熔，聚合物原料和成核剂从前端的喂料口一3喂入，发泡剂从中段的喂料口二4喂入。混合后在加热以及螺杆的剪切力下，各原料被热融并在螺杆混合充分后进入静态混合器5，熔体在静态混合器5中进行深一步均质化和冷却确保熔体温度在120～280℃之间，具体可依照成品物性要求可控。通过熔体泵6(可采用齿轮泵等)的控压和定量输送作用，设定熔体泵6的入口压力在50～200bar之间，控制双螺杆挤塑机2螺膛内熔体压力稳定，使混合发泡剂和成核剂的热熔体中在可控的高压环境中充分混合和均化。通过熔体泵6控压和定量输送功能将高压热熔体稳定的推入挤塑机的模头7，模头7为多孔的孔板结构，其内部含均匀加热设施确保热熔体能稳定通过模头7。被熔体泵6高压送出的热熔体通过模头7的各个孔在水下切粒室8被高速旋转的切粒刀切成豆粒状颗粒，水下切粒室8的切粒刀实际是在水下分切热熔体。10～90℃的工艺水在工艺水泵组件16(包含水泵和水箱等)的作用下产生4～15bar的压力，并通过工艺水进水管9进入水下切粒室8。这样从模头7处挤出的高压热熔体在高压的工艺水下被快速冷却并被切粒刀切成粒状。由于高压热熔体与高压工艺水之间存在压差，而且这种压差可以通过熔体泵6的进口压力和工艺水泵组件16的输送压力来调整，使得整个工艺中被切成粒状的聚合物初始膨胀速率和倍率可控和稳定。因为刚切下的粒状聚合物的冷却时间短和不同配方中材料结晶速度的差异很大，在本工艺中特别设计了多级释压膨胀工艺水管线(此处优选四级)，利用粒状聚合物的外表皮在工艺水中停留时间越长强度越高，承压条件越高的原理，在第一级工艺水管线(即工艺水一级释压管10)中仍然维持4～15bar的水压，此时粒状熔体部分冷却并在压差存在的条件下初步膨胀。在第二级工艺水管线(即工艺水二级释压管11)中通过管线直径的变大和变短将水压降至3～10bar,此时粒状熔体进一步冷却外表面强度上升但压差变大后也会再膨胀。在第三级工艺水管线(即工艺水三级释压管12)中通过管线直 径的变大和变短降低管阻将水压降至2～6bar,此时粒状熔体再次冷却，外表面强度继续上升但压差变大后也再次膨胀但由于颗粒结晶快要完成所以膨胀速率降至很低。在第四级工艺水管线(即工艺水四级释压管13)中还是通过管线直径和长度调整来降低管阻将水压降至1～4bar，此时粒状熔体继续冷却，外表面强度进一步上升但压差仍在变大后也还会膨胀但因为冷却时间足够颗粒外表皮强度已很高并且粒子也基本结晶完成使颗粒外径定型稳固。粒状膨化后的聚合物与水共同进入离心式分离机14中，在这里水和膨化后粒子产品分离，膨胀后的粒子进入振动筛15进入后处理系统并生成膨化成品输出，工艺水从离心式分离机14中流出进入工艺水泵组件16。如此反复，使工艺连续进行。
此外，同样需要指出的是，上述制备方法也只是本发明指出的一种适合制备上述开孔与闭孔结构复合的泡孔结构的优选工艺，除了上述提及的采用螺杆连续发泡的优选工艺外，本发明在同样所提供的基础的可发泡出多种泡孔结构的发泡配方的基础上，同样采用如釜式发泡等常规发泡工艺制备，最后制得的产品同样可具备开孔与闭孔复合的泡孔结构。
下述各实施例中，所采用的聚醚型热塑性聚氨酯来源于拜尔、亨斯迈等厂家；所采用的聚酯型热塑性聚氨酯来源于拜尔、亨斯迈等厂家；所采用的改性低熔点聚酯PET来源于金山石化等；所采用的改性低熔点聚酰胺来源于杜邦、赢创等公司；所采用的PBT来源于金山石化等公司。
实施例1
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，分子量M w在150K～300K(此处的K表示单位千)的聚醚型热塑性聚氨酯，加入比例75％(重量百分数，下同)，分子量M w在50K～100K的聚醚热塑性聚氨酯，加入比例20％，发泡剂为CO 2，加入量4.5％，成核剂为碳酸钙，加入量为0.5％。双螺杆挤塑机长径比L/D＝40，螺杆加热温度160-220℃，静态混合器温度140-180℃，熔体泵入口压力100-120bar，工艺水压力12bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)90-120bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为12bar左右，第二级工艺水管线中的水压控制为8bar左右，第三级工艺水管线中的水压为5bar左右，第四级工艺水管线中的水压控制为2bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料的粒径约为1-3mm左右，材料中，形成的微气囊结构的体积占比约为60-80％左右，开口泡孔结构的体积占比约为10-35％左右。
图2-4为上述实施例1所制得的微气囊聚合物弹性体材料内部的不同尺度的SEM照片，从图中可以看出，材料颗粒中可以看出很明显的由微气囊结构和开口泡孔形成的缠绕网络气道互穿结构；图5-8则为上述实施例1的微气囊聚合物弹性体材料表面的不同尺度的SEM照片，从图中可以看出，上述气道已延伸至材料颗粒表面。
实施例2
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，分子量M w在300K～500K(此处的K表示单位千)的聚醚型热塑性聚氨酯，加入比例60％(重量百分数，下同)，分子量M w在150K～250K的聚醚热塑性聚氨酯，加入比例35％，发泡剂为N 2，加入量4.95％，成核剂为炭黑，加入量为0.05％。双螺杆挤塑机长径比L/D＝56，螺杆加热温度160-220℃，静态混合器温度140-180℃，熔体泵入口压力100-150bar，工艺水压力6bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)90-140bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为6bar左右，第二级工艺水管线中的水压控制为5bar左右，第三级工艺水管线中的水压为3bar左右，第四级工艺水管线中的水压控制为1bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料的粒径约为8-12mm左右，材料中，形成的微气囊结构的体积占比约为30-50％左右，开口泡孔结构的体积占比约为40-60％左右。
实施例3
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，分子量M w在80K～120K(此处的K表示单位千)的聚醚型热塑性聚氨酯，加入比例97％(重量百分数，下同)，分子量M w在20K～50K的聚醚热塑性 聚氨酯，加入比例0.1％，发泡剂为N 2，加入量2.4％，成核剂为滑石粉与改性碳酸钙按质量比1:1的混合物，加入量为0.5％。双螺杆挤塑机长径比L/D＝46，螺杆加热温度160-220℃，静态混合器温度130-170℃，熔体泵入口压力120-180bar，工艺水压力15bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)120-150bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为15bar左右，第二级工艺水管线中的水压控制为10bar左右，第三级工艺水管线中的水压为6bar左右，第四级工艺水管线中的水压控制为4bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料的粒径约为0.6-2mm左右，材料中，形成的微气囊结构的体积占比约为30-45％左右，开口泡孔结构的体积占比约为0.5-10％左右。
实施例4
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，分子量M w在300K～500K(此处的K表示单位千)的聚醚型热塑性聚氨酯，加入比例0.1％(重量百分数，下同)，分子量M w在20K～50K的聚醚热塑性聚氨酯，加入比例97％，发泡剂为N 2，加入量2.8％，成核剂为碳纳米管，加入量为0.1％。双螺杆挤塑机长径比L/D＝48，螺杆加热温度160-220℃，静态混合器温度130-180℃，熔体泵入口压力90-120bar，工艺水压力10bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)80-120bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为10bar左右，第二级工艺水管线中的水压控制为7bar左右，第三级工艺水管线中的水压为4bar左右，第四级工艺水管线中的水压控制为2bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料的粒径约为12-25mm左右，材料中，形成的微气囊结构的体积占比约为20％左右，开口泡孔结构的体积占比约为60-70％左右。
实施例5
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，分子量M w在120K～180K(此处的K表示单位千)的聚醚型热塑性聚氨酯，加入比例70％(重量百分数，下同)，分子量M w在20K～50K的聚醚热塑性聚氨酯，加入比例19.7％，发泡剂为体积比1:1加入的CO 2与N 2，加入量10％，成核剂为碳酸钙与四氟乙烯粉剂按质量比1:1的混合物，加入量为0.3％。双螺杆挤塑机长径比L/D＝40，螺杆加热温度180-240℃，静态混合器温度140-190℃，熔体泵入口压力100-120bar，工艺水压力10bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)90-120bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为10bar左右，第二级工艺水管线中的水压控制为7bar左右，第三级工艺水管线中的水压为4bar左右，第四级工艺水管线中的水压控制为2bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料的粒径约为3-6mm左右，材料中，形成的微气囊结构的体积占比约为60％左右，开口泡孔结构的体积占比约为10％左右。
实施例6
与实施例1相比，绝大部分都相同，除了原材料配方替换为：
分子量M w在200K～300K(此处的K表示单位千)的聚酯型热塑性聚氨酯，加入比例80％(重量百分数，下同)，分子量M w在50K～100K的聚酯型热塑性聚氨酯，加入比，加入比例18.9％，发泡剂为体积比1:1加入的CO 2与N 2，加入量1％，成核剂为碳酸钙与四氟乙烯粉剂按质量比1:1的混合物，加入量为0.1％。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为70-80％左右，开口泡孔结构的体积占比约为15-30％左右。
实施例7
与实施例1相比，绝大部分都相同，除了原材料配方替换为：
邵氏硬度80A的聚酯型热塑性聚氨酯加入量为80％(重量百分数，下同)，邵氏硬度为30A的聚酯型热塑性聚氨酯加入量为19.5％，发泡剂选用CO 2与N 2按重量比1:1的混合，其总加入量为0.4％，成核剂选用碳纳米管、滑石粉和碳酸钙的 混合，总加入量为0.1％。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为70-80％左右，开口泡孔结构的体积占比约为15-30％左右。
实施例8
与实施例7相比，绝大部分都相同，除了原材料配方替换为：
邵氏硬度75D的聚酯型热塑性聚氨酯加入量为70％(重量百分数，下同)，邵氏硬度为85A的聚酯型热塑性聚氨酯加入量为27.5％，发泡剂选用CO 2与N 2按重量比1:1的混合，其总加入量为2％，成核剂选用碳纳米管、滑石粉和碳酸钙的混合，总加入量为0.5％。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为60-70％左右，开口泡孔结构的体积占比约为25-40％左右。
实施例9
与实施例7相比，绝大部分都相同，除了原材料配方中高硬度聚酯型热塑性聚氨酯的邵氏硬度替换为90A，低硬度聚酯型热塑性聚氨酯的邵氏硬度替换为50A。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为70-80％左右，开口泡孔结构的体积占比约为15-30％左右。
实施例10
根据上述如图1的工艺流程按照以下原料配方与工艺条件来制备本发明的热塑性微气囊聚合物弹性体材料：
其中，改性低熔点聚酯PET加入比例60％(重量百分数，下同)，聚酯型聚氨酯加入比例37％(改性低熔点聚酯PET与聚酯型聚氨酯的熔点差在20℃)，成核 剂为炭黑，加入量为0.5％，发泡剂为CO2与N2的混合，其加入量为2.5％。
双螺杆挤塑机长径比L/D＝52，螺杆加热温度220-280℃，静态混合器温度160-200℃，熔体泵入口压力100-150bar，工艺水压力15bar左右，控制释压压差(即模头出口的高压热熔体与水下切粒室中的工艺水的压力差)130-180bar。多级释压膨胀工艺水管线中，第一级工艺水管线中的水压控制为15bar左右，第二级工艺水管线中的水压控制为12bar左右，第三级工艺水管线中的水压为8bar左右，第四级工艺水管线中的水压控制为4bar左右。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为50-80％左右，开口泡孔结构的体积占比约为5-50％左右。
实施例11
与实施例10相比，除了将改性低熔点聚酯PET替换为改性低熔点聚酰胺(PA)外，其余均一样。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为50-80％左右，开口泡孔结构的体积占比约为5-50％左右。
实施例12
与实施例10相比，除了将改性低熔点聚酯PET替换为PBT外，其余均一样。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构，材料中，形成的微气囊结构的体积占比约为50-80％左右，开口泡孔结构的体积占比约为5-50％左右。
实施例13-15
与实施例1相比，除了将发泡剂分别改为正丁烷、正戊烷或异戊烷外，其余均一样。
以上实施例13-实施例15在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构。
实施例16
与实施例1相比，除了本实施例中进入水下切粒室的切粒直接被温度40-50℃，压力为4-8bar的基本稳定温度与压力的工艺水带出并释压冷却成型外，其余均一样。
最后，在振动筛处制得的热塑性微气囊聚合物弹性体材料同样具备微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，参考图2-图8中显示的泡孔结构。但是，与实施例1的发泡颗粒相比，本实施例的发泡颗粒有部分存在泡孔击穿现象。
实施例17
与实施例1相比，除了本实施例采用常规釜式发泡工艺，发泡温度约为150℃左右，压力约为15Mpa左右。
最后，制备得到的发泡颗粒同样可具备参考图1-8中发泡颗粒的微气囊结构(闭孔结构)与开孔结构复合的泡孔结构，但是，泡孔结构不太稳定，容易收缩。
对比例1
与实施例1相比，除了本实施例中聚合物原料(聚醚型热塑性聚氨酯)全部采用150K～300K聚醚热塑性聚氨酯外，其余均一样。
对比例2
与实施例7相比，除了本实施例中聚合物原料全部采用邵氏硬度80A的聚酯型热塑性聚氨酯外，其余均一样。
对比例3
与实施例10相比，除了本实施例中聚合物原料全部采用同样的改性低熔点聚酯PET(即没有聚酯型聚氨酯加入)外，其余均一样。
最后，将对比例1-对比例3三个对比例所制备得到的发泡材料检测分析其泡孔结构，这三个对比例最后所得到的发泡颗粒的表皮均为连续表皮，且对其颗粒切开扫描其内部可发现基本全为闭孔结构，且并没有如实施例1图5-图8所示的延 伸至表皮的开孔结构，且发泡倍率相比于两种聚合物原料混合的配方而言，明显要低。
综合以上实施例以及对比例可知，相比于对比例采用单一物性聚合物作为原料所制备得到的纯闭孔结构的发泡颗粒制品而言，本发明通过对发泡颗粒片配方进行改进，采用两种物性不同的聚合物作为原料，再结合发泡过程中发泡剂在两种聚合物中发泡能力的差别，制备得到了开孔与闭孔相复合的泡孔结构的发泡颗粒。
前面的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其范围之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种热塑性微气囊聚合物弹性体材料，其特征在于，其配方包括以下重量百分比含量的组分：支撑骨架聚合物材料0.1-97％，耐压回弹聚合物材料0.1-97％，成核剂0.01～0.5％，发泡剂0.1～10％。
  2. 根据权利要求1所述的一种热塑性微气囊聚合物弹性体材料，其特征在于，所述的支撑骨架聚合物材料为高分子量、高硬度、高结晶或高极性聚合物材料，所述的耐压慢回弹聚合物材料为与支撑骨架聚合物材料相对应的低分子量、低硬度、低结晶至无定形态、低极性至无极性聚合物材料。
  3. 根据权利要求2所述的一种热塑性微气囊聚合物弹性体材料，其特征在于，所述的支撑骨架聚合物材料为高分子量热塑性聚氨酯，其对应的耐压回弹聚合物材料为低分子量热塑性聚氨酯；
    或所述的支撑骨架聚合物材料为高硬度热塑性聚合物弹性体，其对应的耐压慢回弹聚合物材料为低硬度热塑性聚合物弹性体；
    或所述的支撑骨架聚合物材料为聚酰胺或聚酯，其对应的耐压慢回弹聚合物材料为热塑性聚氨酯。
  4. 根据权利要求3所述的一种热塑性微气囊聚合物弹性体材料，其特征在于，所述的高分子量聚氨酯的分子量M w为8×10 4～5×10 5，低分子量聚氨酯的分子量M w为2×10 4～2.5×10 5；
    高硬度热塑性聚合物弹性体的邵氏硬度为80A～75D，低硬度热塑性聚合物弹性体的邵氏硬度为30～85A；
    聚酯或聚酰胺分别为改性低熔点聚酯或改性低熔点聚酰胺，并控制支撑骨架聚合物材料和耐压回弹聚合物材料的熔点差在20℃内。
  5. 根据权利要求1所述的一种热塑性微气囊聚合物弹性体材料，其特征在于，所述的成核剂选自碳纳米管、二氧化硅、滑石粉、改性碳酸钙、炭黑或四氟乙烯粉剂中的至少一种；
    所述的发泡剂选自CO 2、N 2、正丁烷、正戊烷或异戊烷中的至少一种。
  6. 根据权利要求1所述的一种热塑性微气囊聚合物弹性体材料，其特征在于，所述的聚合物弹性体材料为均匀的球形颗粒，其粒径为0.6-25mm。
  7. 如权利要求1-6任一所述的热塑性微气囊聚合物弹性体材料的制备方法， 其特征在于，包括以下步骤：
    (1)将支撑骨架聚合物材料、耐压慢回弹聚合物材料和成核剂从双螺杆挤塑机前端加料口喂入，发泡剂从双螺杆挤塑机中段加料口喂入，使各原料热熔混合充分后，再进入静态混合器进一步均质化，接着再经熔体泵控压和定量输送；
    (2)被熔体泵送出的热熔体通过模头进入水下切粒室切粒，并由工艺水带出分离，所得颗粒筛选干燥后即形成目的产品。
  8. 根据权利要求7所述的一种热塑性微气囊聚合物弹性体材料的制备方法，其特征在于，步骤(1)中双螺杆挤塑机的温度为160～300℃，双螺杆挤出机长径比为32-56；
    静态混合器内的温度设定为120-280℃，熔体泵的入口压力50-200bar，并同时控制经模头挤出的热熔体压力与水下切粒室中工艺水的压力之差为70-120bar。
  9. 根据权利要求7所述的一种热塑性微气囊聚合物弹性体材料的制备方法，其特征在于，步骤(2)中水下切粒室中的工艺水温度为10-90℃，压力为4-15bar；
    切粒被工艺水带出时，经过压力逐级降低的多级释压膨胀工艺水管线输送。
  10. 根据权利要求9所述的一种热塑性微气囊聚合物弹性体材料的制备方法，其特征在于，步骤(2)中多级释压膨胀工艺水管线为多级工艺水管线，其中，第一级工艺水管线的水压力保持与进入水下切粒室的工艺水压力一致。
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