CN108864662B - Thermoplastic polyether ester elastomer foam material and preparation method thereof - Google Patents

Thermoplastic polyether ester elastomer foam material and preparation method thereof Download PDF

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CN108864662B
CN108864662B CN201810824880.2A CN201810824880A CN108864662B CN 108864662 B CN108864662 B CN 108864662B CN 201810824880 A CN201810824880 A CN 201810824880A CN 108864662 B CN108864662 B CN 108864662B
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polyether ester
tpee
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CN108864662A (en
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陈乔健
郭杨龙
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Nantong Deyi New Material Co ltd
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
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    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

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Abstract

The invention relates to a thermoplastic polyether ester elastomer foam material and a preparation method thereof, wherein the foam material is prepared from the following raw materials in parts by weight: 50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material, 0.05-2 parts of nucleating agent and 0.1-5 parts of foaming agent, wherein when the addition amount of the modified polymer material is 0, the melting temperature T of the polyether ester TPEE is2And Vicat softening point temperature T1Difference value T of2‑T1Not less than 30 ℃. Compared with the prior art, the invention provides a formula of TPEE capable of being foamed continuously and a continuous foaming process, and solves the problem that the conventional TPEE is difficult to prepare a foaming material with stable performance, particularly difficult to foam continuously.

Description

Thermoplastic polyether ester elastomer foam material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer foam materials, and relates to a thermoplastic polyether ester TPEE elastomer foam material and a preparation method thereof.
Background
Thermoplastic polymer elastic materials are widely applied to various production and living facilities, equipment, tools and consumables, and the requirement of material light weight is more and more urgent along with the requirements of social development on environmental protection, energy conservation, consumption reduction and the like. Thermoplastic polymer elastic materials are also largely started to be subjected to lightweight experiments and verifications and are continuously popularized and applied. For example, polypropylene PP foam, polyethylene PE foam, polystyrene PS foam, polyester PET foam, polyamide PA foam, polyurethane TPU foam, and the like. The thermoplastic polyether ester elastomer TPEE has low melt strength, the skin polyester part is quickly crystallized when the melt expands under the pressure relief, the polyether part is cracked and air-leaked, and the expansion time of the polyether ester TPEE is greatly influenced, so that the foaming multiplying power and the cell structure are influenced, the application of TPEE foaming materials is further limited, and the conventional TPEE can only be carried out by processes such as kettle type foaming and the like.
At present, kettle type foaming has the following defects: 1) the foaming kettle has large volume, high temperature of more than or equal to 120 ℃, high pressure of more than or equal to 12Mpa and poor process safety condition. 2) Low efficiency, and long retention time of the elastomer in the foaming kettle due to low permeability of the physical foaming agent caused by the molecular structure of the TPEE. 3) The yield is low, and the pressure drop rate at each point in the kettle is seriously different due to the vortex action of the pressure release port in the pressure release process, so that the foaming ratio difference of the material is large, and the material with the similar foaming ratio only accounts for 50-80% of the total amount. 4) The kettle type foaming process line limits that the process has no way or means to differentially adjust the temperature of the outer wall and the inner core of the foaming material, so that the material is actually in a softening state or a high-elastic state instead of a viscous state or a melting state in the kettle, the outer wall of the material is a bubble core with a continuous phase wrapping the inner core, the bubble structure cannot be adjusted according to market demands, the foaming body can only be in a full-closed-pore structure, and the downstream application path of the single foaming material in the full-closed-pore structure is narrow.
However, the TPEE material has many advantages of physical properties, such as high wear resistance, higher heat resistance, high tensile modulus and compression modulus, excellent fatigue resistance and the like, so that the TPEE material has a very wide application prospect. Therefore, if a continuous foaming process such as extrusion foaming, casting foaming and the like of the TPEE can be provided, the problems of low efficiency, non-uniform particle size of foaming particles and difficult adjustment of a cell structure of the traditional kettle type foaming can be solved, and the application range of the TPEE foaming material can be greatly widened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a thermoplastic polyether ester elastomer foaming material and a preparation method thereof, particularly provides a formula and a continuous foaming process of TPEE, and solves the problem that the conventional TPEE is difficult to prepare a foaming material with stable performance, particularly difficult to foam continuously.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a thermoplastic polyether ester elastomer foaming material which is prepared from the following raw material components in parts by weight: 50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material, 0.05-2 parts of nucleating agent and 0.1-5 parts of foaming agent, wherein when the addition amount of the modified polymer material is 0, the melting temperature T of the polyether ester TPEE is2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1≥30℃。
Further, elongation at break of the polyether ester TPEE (test specimen)Quasi ISO527) ≥ 300%, the addition amount of the modified polymer material can be zero under the selection of the polyether ester TPEE under the physical property conditions. Preferably, the tensile strength (test standard ISO527) is more than or equal to 15Mpa, so that the melt cannot be completely punctured by the high-speed expanded gas core when the material is foamed under the pressure relief (particularly when the foaming multiplying power is more than or equal to 4 times), and the tensile strength of the foamed material can be ensured, namely more than or equal to 1N/mm2(GB/T528). Meanwhile, the limit on the elongation at break is to ensure that more gas cores can be wrapped by the material in the fluidity and extensibility in the viscous state, so as to meet the foaming requirement. And T2-T1When the temperature is more than or equal to 30 ℃, the melt has enough temperature interval under the forced cooling, so that the gas core foaming (namely melt expansion) and the cooling shaping (namely cell wall skinning shaping) have enough time difference to ensure the process operability.
When the polyether ester TPEE is a conventional general product, the physical properties of which are out of the above-defined standard ranges, the addition amount of the modified polymer material is not zero, and is preferably about 1 to 50 parts.
In a preferred embodiment of the present invention, the modified polymer material is selected from one or more of polyamide 6, polyamide 9, polyamide 10, polyamide 11, polyamide 12, nylon elastomer, low-melting point co-nylon, polyether type thermoplastic polyurethane elastomer, polyester type thermoplastic polyurethane elastomer, thermoplastic styrene-butadiene hydrogenated copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester, PBAT, PTT, PET, and the like.
Among the different modified polymer materials, other materials with low or amorphous nylon crystallinity such as polyamide 6I, polyamide 9, polyamide 10, polyamide 11, polyamide 12, etc. have the following advantages in modification: 1) the regular crystal area of the TPEE is damaged, the crystallization temperature of the blending material is reduced, so that the physical foaming agent is easy to permeate, the skinning speed is not too high when the melt is cooled, and the continuous extrusion foaming and underwater cutting foaming shaping or in-mold foaming shaping are facilitated; 2) because of the partial compatibility between the modified material and the TPEE, a phase boundary and a phase gap exist during blending, so that a gas core can conveniently enter the phase boundary, and a special air passage along the phase boundary and the phase gap is designed to change a cell structure.
Polyester or polyether thermoplastic polyurethanes have the following advantages when modified: 1) the strength of TPEE in the melt is improved, the melt cannot be completely broken down by gas nuclei during foaming, and particularly, when the temperature of the melt and the temperature of granulating water are increased to obtain higher foaming ratio, the strength of the melt is not very high, and the foam breaking rate of a foaming material is very high; 2) the regular crystal area of the TPEE is damaged, the crystallization temperature of the blending material is reduced, and the physical foaming agent is easy to permeate and the skinning speed of the melt is not too high when the temperature of the melt is reduced. Is beneficial to extrusion molding continuous foaming and underwater cutting foaming shaping or foaming shaping in a die.
The modification advantages of the grafted SEBS, the grafted rubber, the olefin elastomer containing a polar side chain and the like are as follows: 1) the grafted rubber or polyolefin, the rubber containing polar side chains and the elastomer are mostly in an amorphous state or a semicrystalline or noncrystalline polymer, so that the continuity of a continuous phase and a hard segment of the TPEE can be destroyed, and the melt after modification can still maintain enough strength of the melt at high temperature; 2) because the TPEE and the rubber polymer are only partially compatible, the phase boundary is obvious, the permeability of the foaming agent is greatly different, and a proper cell structure and an opening-closing ratio can be designed.
In a preferred embodiment of the invention, the nucleating agent is one or more of modified nano calcium carbonate, 2-10 μm talcum powder, modified montmorillonite, silicon dioxide and PMMA powder
Further, the blowing agent is preferably 0.1 to 2 parts. Further, the nucleating agent is preferably 0.1-0.5%.
In a preferred embodiment of the present invention, the foaming agent is one or a combination of several of freon, n-butane, n-pentane, isopentane, carbon dioxide or nitrogen.
In a preferred embodiment of the invention, no more than 50 parts of a cross-linking agent is also added to the raw material formulation. More preferably, the cross-linking agent is one or a combination of several of polyisocyanate group-containing polymer, polyepoxy group-containing polymer, polyhydroxy group-containing polymer or polycarboxy group-containing polymer. The addition of the cross-linking agent can generate cross-linking points among molecular chains of the TPEE, thereby improving the melt strength at high temperature and the physical properties of the foamed material such as: tensile strength, tear strength, elastic recovery, and the like.
Even more preferably, the crosslinking agent is a mixture of a polyisocyanate group-containing polymer and a polyol group-containing polymer. At this time, the tear strength of the resulting expanded beads was significantly improved by about 50% or more.
Furthermore, according to the physical property requirement of the thermoplastic polyether ester elastomer foaming material to be prepared, auxiliary functional additives such as one or more of antioxidants (antioxidant 1010, antioxidant 1135, antioxidant 1098, DLTP and the like), UV absorbers (UV327, UV328, UV329 and the like), hydrolysis-resistant agent carbodiimide, a lubricant or a release agent polyamide wax, oxidized polyethylene wax, oxidized polypropylene wax and the like can be added into the formula, and the addition amount is about 0.1-10 parts, preferably 0.5-1.5 parts.
The second purpose of the invention is to provide a preparation method of the thermoplastic polyether ester elastomer foaming material, which comprises the following steps:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder, and fully melting and homogenizing;
(2): injecting a foaming agent into the homogenized mixture obtained in the step (1), and continuously homogenizing to obtain a homogenized melt;
(3): and extruding the homogenized melt into a melt pump, conveying the melt into a die head, extruding and foaming to obtain the foaming material.
In a preferred embodiment of the invention, in step (1), the conditions for heating and melting the polyether ester TPEE and the other raw material components than the blowing agent in the twin-screw extruder are: the heating temperature is within the temperature range of + -50 ℃ of the melting temperature of the polyetherester TPEE. When the extrusion temperature is lower than the melting temperature, the material is in a high-elasticity state above the softening point, in this case, under the strong shearing of the screw, the materials can be homogenized, in addition, the heating temperature of the screw does not represent the melt temperature, and the hot melting effect caused by the shearing force of the screw also needs to be considered.
In a preferred embodiment of the present invention, in step (2), the melt pressure in the material mixing zone after the addition of the foaming agent in the twin-screw extruder is 20bar to 200 bar. The melt pressure is the pressure in a specific region of the extruder, and the corresponding melt temperature requires a corresponding melt pressure to ensure that the physical blowing agent can penetrate into the melt and be encapsulated by the melt in a shorter time. Too high a melt pressure means too much penetration of the blowing agent, which becomes a plasticizer for the melt at high temperatures and the melt strength is greatly reduced. The melt pressure is too low and the blowing agent cannot ensure a sufficient penetration rate in the extruder, which affects the foaming effect.
In a preferred embodiment of the present invention, in the step (3), the temperature of the homogenized melt extruded into the melt pump is 140 to 240 ℃ and the pressure is 0.2 to 20 MPa.
In a preferred embodiment of the invention, the internal structural arrangement in the twin-screw extruder ensures: in the extrusion process, the screw extrusion molding mixing area after the foaming agent is added and the screw extrusion molding mixing area before the foaming agent is added are sealed and backflow is stopped.
In a preferred embodiment of the invention, the melt of the extrusion die head directly enters an underwater pelletizing chamber for foaming, the pressure in the underwater pelletizing chamber is 0.1-1.2Mpa, and the temperature of the process cooling water is 40-100 ℃. At this time, the pressure of the underwater pelletizing chamber as the low pressure side and the temperature of the process cooling water need to be ensured to have enough pressure and temperature difference with the high pressure side of the die. The pressure difference between the melt and the pressure in the underwater pelletizing chamber affects the pressure release speed during foaming and thus the size and density of the cells, and the temperature difference is understood to be the temperature difference between the melt and the water in the underwater pelletizing chamber, i.e. the temperature difference affects the melt skinning time, the foam wall setting time and the time for which the cells can expand.
In a preferred embodiment of the invention, the melt of the extrusion die head directly enters a shaping mold for foaming, the surface temperature of the shaping mold is 30-100 ℃, and the pressure is 0.5-5 Mpa, preferably 0.8-3.5 Mpa.
Compared with the prior art, the invention has the following characteristics:
(1) in the case that the polyether ester TPEE is not successfully injected with a physical foaming agent in the world due to the high crystallization temperature and the nucleation forming speed of the polyether ester TPEE and is prepared into TPEE foaming bead particles in an underwater granulation process, the invention limits the key physical property data (such as melting temperature and the like) of the polyether ester TPEE which can be extruded and foamed, can select raw materials from the types of the commercially available TPEE according to the physical property requirement recorded by the invention to ensure the proper extrusion and foaming process, or can obtain a TPEE copolymer which meets the key physical property material recorded by the invention and obtains the proper extrusion and foaming process by material modification.
(2) The pressure of the melt on the high-pressure side of the die head (namely the side of a melting pump) and the pressure of the melt on the low-pressure side of the die head (namely the side of the die head contacted with an underwater granulating chamber or a shaping die) are controlled to ensure the pressure release speed of the material so as to control the size of the cells, so that the situation that the melt is broken before unshaped due to the fact that the pressure difference is too large and the gas nuclei expand too fast is avoided, the particles with large proportion of broken bubbles or broken perforation channels on the outer surface or inside the particles are obtained, and the cooling and shaping are carried out even if the pressure difference is too small.
(3) The temperature of a melt in the extruder is controlled to be within +/-50 ℃ of the melting temperature of the blending material, and the temperature of the granulating water in the granulating water chamber is controlled to be within 40-100 ℃, preferably 60-80 ℃, so that the cooling and shaping time of the foamed particles can be accurately controlled, and the excellent appearance and the proper particle size are obtained.
(4) Or the pressure of the melt on the high-pressure side of the die head and the pressure in the die runner (namely the low-pressure side of the die head) are controlled to ensure the pressure release speed of the material so as to control the size of the foam pores, so that the large area of the outer surface of the melt is not punctured due to too high expansion of the large-pressure-difference nuclei, and the outer surface of the melt is not cooled and shaped due to too low expansion of the small-pressure-difference nuclei, so that the difference between the appearance size of the finished product and the design size.
(5) Or controlling the temperature of the melt in the extruder to be +/-50 ℃ of the melting temperature of the blending material and simultaneously controlling the temperature of each surface of the die to be 30-100 ℃, so that the cooling and shaping time of the foaming particles can be accurately controlled, and the qualified surface and size of the product can be obtained.
(6) Through the process combination of a multi-stage double screw, a multi-stage melt pump, a dynamic mixer, a static mixer and the like, the applicability and the universality of the material in the process can be flexibly adjusted, and the modular combination of the process can be realized, so that the problem of limited foaming of the TPEE in the conventional process environment is solved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
A thermoplastic polyether ester elastomer foaming material comprises the following necessary raw materials: 80 parts of polyether ester TPEE, 0.5 part of nucleating agent and 1.5 parts of foaming agent. Wherein the melting temperature T of the polyether ester TPEE2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T175 ℃, tensile strength (test standard ISO527) 25Mpa, elongation at break (test standard ISO527) approximately equal to 850%, nucleating agent modified nano calcium carbonate and foaming agent carbon dioxide.
In this embodiment, the underwater granulation foaming is preferably adopted to prepare the foaming material, and the specific process is as follows:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder, controlling the temperature to be the melting temperature of the material, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and homogenizing the TPEE and other materials fully through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 10Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 100bar, and finely regulating the temperature of the melt entering the melt pump to be 180 ℃ from the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and enters the grain cutting water chamber through the die head, the TPEE melt is rapidly sheared into melt bead-shaped particles in the grain cutting water chamber by an underwater grain cutter, the pressure in the grain cutting water chamber is controlled to be 0.6Mpa, the melt enters the low pressure side (0.6Mpa) contacting the grain cutting water chamber at the high pressure side (namely, the side contacting with the melt pump, 10Mpa) of the die head, and due to pressure release, in 0.01-1 second, a gas core wrapped by the melt which is cut into bead-shaped particles by the grain cutting knife rapidly expands in the grain cutting water chamber and the grain cutting water pipeline and is rapidly cooled by grain cutting water. The expansion process can be controlled by the length and the diameter of a grain cutting water pipeline and a booster pump, the grain cutting water pressure is 0.6Mpa, and meanwhile, the temperature of cooling process water is finely adjusted to 70 ℃ by a grain cutting water storage tank heater, a grain cutting water cooler and the like, so that the cooling time of the bead-shaped particles is adjusted, and the foaming ratio of the TPEE beads is proper.
The thermoplastic polyether ester elastomer foam material in the embodiment can also be prepared by adopting other conventional puffing preparation processes.
Comparative example 1
Compared with example 1, the melting temperature T of the polyether ester TPEE is determined in most cases with the exception that a common commercial product is used2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1＝20℃。
Comparative example 2
Compared with example 1, the elongation at break of the polyether ester TPEE used in this example is about 150%.
Comparative example 3
In comparison with example 1, the same applies for the most part, except that in this example the melt pressure in the twin-screw extruder was instead controlled at 10 bar.
Comparative example 4
In comparison with example 1, the same applies for the most part, except that the melt pressure in the twin-screw extruder was instead controlled at 250 bar.
The foams obtained in the above examples and comparative examples were observed and examined, and the specific results are shown in Table 1 below.
TABLE 1 Properties of the TPEE foams obtained in the examples
Figure GDA0002522547050000071
Figure GDA0002522547050000081
As can be seen from the data of the example 1 and the comparative examples 1 to 5, the invention respectively limits the physical properties of the TPEE, such as melting temperature, Vicat softening point temperature difference, elongation at break and the like, so that the finally prepared foaming product is improved in the aspects of foaming operability, foaming multiplying power, foaming product molding and the like, and is further improved from one side or multiple sides respectively, and the problem that the existing TPEE foaming particles are difficult to realize continuous foaming is solved.
Example 2
A thermoplastic polyether ester elastomer foaming material comprises the following necessary raw materials: 50 parts of polyether ester TPEE, 0.05 part of nucleating agent and 0.1 part of foaming agent. Wherein the melting temperature T of the polyether ester TPEE2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1The composite material is prepared by the following steps of preparing a composite material, wherein the composite material is prepared by the following steps of (1) about 30 ℃, about 30Mpa of tensile strength (test standard ISO527), about 600% of elongation at break (test standard ISO527), 2-10 um of talcum powder serving as a nucleating agent and nitrogen serving as a foaming agent.
In the embodiment, the foam material is prepared by underwater granulating and foaming, and the specific process is as follows:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder together, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and the TPEE and other materials are fully homogenized through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 0.2Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 20bar, and finely regulating the temperature of the melt entering the melt pump to be 210 ℃ from the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and enters the grain cutting water chamber through the die head, TPEE melt is rapidly sheared into melt bead-shaped particles in the grain cutting water chamber by an underwater grain cutter, the pressure in the grain cutting water chamber is controlled to be 0.1Mpa, the melt enters the low-pressure side (0.1Mpa) contacting the grain cutting water chamber at the high-pressure side (namely, the side contacting with the melt pump, 0.2Mpa) of the die head, and due to pressure release, in 0.01-1 second, gas nuclei wrapped by the melt which is cut into bead-shaped particles by the grain cutting knife rapidly expand in the grain cutting water chamber and grain cutting water pipeline and are rapidly cooled by grain cutting water. The expansion process can be controlled by the length and the diameter of a grain cutting water pipeline and a booster pump, the grain cutting water pressure is 0.1Mpa, and meanwhile, the temperature of cooling process water is finely adjusted to 80 ℃ by a grain cutting water storage tank heater, a grain cutting water cooler and the like, so that the cooling time of the bead-shaped particles is adjusted, and the foaming ratio of proper TPEE beads is obtained.
The TPEE foaming bead prepared by the embodiment has continuous skin, stable particle shape without collapse, uniform particle size, foaming multiplying power of about 2-3 times and no collapse after secondary forming. When the process water pressure and temperature are changed, the adjustable foaming multiplying power range of the particles is about 1-7 times.
Example 3
A thermoplastic polyether ester elastomer foaming material comprises the following necessary raw materials: 95 parts of polyether ester TPEE, 0.1 part of nucleating agent and 5 parts of foaming agent. Wherein the melting temperature T of the polyether ester TPEE2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1The composite material is characterized by comprising the following components in percentage by volume of more than or equal to 30 ℃, tensile strength (test standard ISO527) of more than or equal to 15Mpa, elongation at break (test standard ISO527) of more than or equal to 300%, a nucleating agent which is modified montmorillonite, and a foaming agent which is a mixture of carbon dioxide and nitrogen in a volume ratio of 1: 1.
In the embodiment, the foam material is prepared by underwater granulating and foaming, and the specific process is as follows:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder together, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and the TPEE and other materials are fully homogenized through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 20Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 200bar, and finely regulating the temperature of the melt entering the melt pump to be 230 ℃ from the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and enters the grain cutting water chamber through the die head, the TPEE melt is rapidly sheared into melt bead-shaped particles in the grain cutting water chamber by an underwater grain cutter, the pressure in the grain cutting water chamber is controlled to be 1.2Mpa, the melt enters the low pressure side (1.2Mpa) contacting the grain cutting water chamber at the high pressure side (namely, the side contacting with the melt pump, and 20Mpa) of the die head, and due to pressure release, in 0.01-1 second, a gas core wrapped by the melt which is cut into bead-shaped particles by the grain cutting knife rapidly expands in the grain cutting water chamber and the grain cutting water pipeline and is rapidly cooled by grain cutting water. The expansion process can be controlled by the length and the diameter of a grain cutting water pipeline and a booster pump, the grain cutting water pressure is 1.2Mpa, and meanwhile, the temperature of cooling process water is finely adjusted by a grain cutting water storage tank heater, a grain cutting water cooler and the like to be 95 ℃, so that the cooling time of the bead-shaped particles is adjusted, and the foaming ratio of proper TPEE beads is obtained.
The TPEE foaming bead prepared by the embodiment has continuous skin, stable particle shape without collapse, uniform particle size, foaming multiplying power of about 4-6 times and no collapse after secondary forming. When the process water pressure and temperature are changed, the adjustable foaming multiplying power range of the particles is about 1-8 times.
Example 4
A thermoplastic polyether ester elastomer foaming material comprises the following necessary raw materials: 45D polyether ester TPEE70 parts, nucleating agent 0.2 part and foaming agent 0.5 part. Wherein the melting temperature T of the polyether ester TPEE2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1Not less than 30 ℃, and the tensile strength (test standard ISO527) not less than 15Mpa, the elongation at break (test standard ISO527) is more than or equal to 300 percent, the nucleating agent is the mixture of silicon dioxide and modified montmorillonite according to the mass ratio of 1:1, and the foaming agent is the mixture of butane and carbon dioxide according to the volume ratio of 1: 1.
In the embodiment, the foam material is prepared by underwater granulating and foaming, and the specific process is as follows:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder together, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and the TPEE and other materials are fully homogenized through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 5Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 80bar, and finely regulating the temperature of the melt entering the melt pump to be 220 ℃ from the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and enters the grain cutting water chamber through the die head, the TPEE melt is rapidly sheared into melt bead-shaped particles in the grain cutting water chamber by an underwater grain cutter, the pressure in the grain cutting water chamber is controlled to be 0.3Mpa, the melt enters the low pressure side (0.3Mpa) contacting the grain cutting water chamber at the high pressure side (namely, the side contacting with the melt pump and 8Mpa) of the die head, and due to pressure release, in 0.01-1 second, a gas core wrapped by the melt which is cut into bead-shaped particles by the grain cutting knife rapidly expands in the grain cutting water chamber and the grain cutting water pipeline and is rapidly cooled by grain cutting water. The expansion process can be controlled by the length and the diameter of a grain cutting water pipeline and a booster pump, the grain cutting water pressure is 0.3Mpa, and meanwhile, the temperature of cooling process water is finely adjusted by a grain cutting water storage tank heater, a grain cutting water cooler and the like to be 90 ℃, so that the cooling time of the bead-shaped particles is adjusted, and the foaming ratio of the TPEE beads is proper.
The TPEE foaming bead prepared by the embodiment has continuous skin, stable particle shape without collapse, uniform particle size, foaming multiplying power of about 4-6 times and no collapse after secondary forming. When the process water pressure and temperature are changed, the adjustable foaming multiplying power range of the particles is about 1-12 times.
Example 5
A thermoplastic polyether ester elastomer foaming material comprises the following necessary raw materials: 88 parts of polyether ester TPEE, 2 parts of nucleating agent and 2 parts of foaming agent. Wherein the melting temperature T of the polyether ester TPEE2(test Standard ISO11357) and Vicat softening Point temperature T1(test Standard ISO 306) difference T2-T1The composite material has the advantages of more than or equal to 30 ℃, tensile strength (test standard ISO527) more than or equal to 15Mpa, elongation at break (test standard ISO527) more than or equal to 300 percent, a nucleating agent of PMMA powder and a foaming agent of carbon dioxide.
In the embodiment, the foam material is prepared by underwater granulating and foaming, and the specific process is as follows:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder together, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and the TPEE and other materials are fully homogenized through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 15Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 150bar, and finely regulating the temperature of the melt entering the melt pump to be 170 ℃ through the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and enters the grain cutting water chamber through the die head, the TPEE melt is rapidly sheared into melt bead-shaped particles in the grain cutting water chamber by an underwater grain cutter, the pressure in the grain cutting water chamber is controlled to be 0.7Mpa, the melt enters the low pressure side (0.7Mpa) contacting the grain cutting water chamber at the high pressure side (namely the side contacting with the melt pump, 15Mpa) of the die head, and due to pressure release, in 0.01-1 second, a gas core wrapped by the melt which is cut into bead-shaped particles by the grain cutting knife rapidly expands in the grain cutting water chamber and the grain cutting water pipeline and is rapidly cooled by grain cutting water. The expansion process can be controlled by the length and the diameter of a grain cutting water pipeline and a booster pump, the grain cutting water pressure is 0.7Mpa, and meanwhile, the temperature of cooling process water is finely adjusted at 60 ℃ by a grain cutting water storage tank heater, a grain cutting water cooler and the like, so that the cooling time of the bead-shaped particles is adjusted, and the foaming ratio of the TPEE beads is proper.
The TPEE foaming bead prepared by the embodiment has continuous skin, stable particle shape without collapse, uniform particle size, foaming multiplying power of about 6 to 7 times and no collapse after secondary forming. When the process water pressure and temperature are changed, the adjustable foaming multiplying power range of the particles is about 1-12 times.
Example 6
Compared with the embodiment 1, the polyether ester TPEE has the same structure, except that the conventional commercial base material is adopted in the polyether ester TPEE, and 30 parts of modified polymer material is also added, wherein the modified polymer material is polyether type thermoplastic polyurethane elastomer.
The TPEE foamed bead prepared by the embodiment has an obvious open-cell and closed-cell composite structure, excellent elastic recovery performance during kneading, and no collapse during secondary molding. In addition, the expansion ratio range of the expandable beads which can be adjusted by adjusting the conditions such as the melting temperature and the temperature of the process water can be increased to about 1 to 15 times. And the foamed article obtained is substantially free from the problem of collapse even at a high expansion ratio of 10 to 15 times.
Example 7
Compared to example 6, the majority was the same except that the modified polymeric material was added in an amount of 50 parts in this example.
The performance of the article of this example was substantially the same as that of example 6, except that the ratio of open to closed cell volume was varied.
Example 8
Compared to example 6, the majority was the same except that the modified polymeric material was added in an amount of 1 part in this example.
The TPEE foamed bead prepared by the embodiment has an obvious open-cell and closed-cell composite structure, excellent elastic recovery performance during kneading, and no collapse during secondary molding. In addition, the expansion ratio range of the expandable particles which can be adjusted by adjusting the conditions such as melting temperature, process water temperature and the like can be increased to about 1-11 times, and secondary molding does not collapse. And the foamed article obtained is substantially free from the problem of collapse even at a high expansion ratio of 9 to 11 times.
Example 9
Compared with the embodiment 6, the modified polymer is mostly the same, except that one of nylon materials such as polyamide 6, polyamide 9, polyamide 10, polyamide 11, polyamide 12 and the like is selected as the modified polymer material in the embodiment.
The TPEE foaming beads modified by different nylon materials prepared by the embodiment all have obvious open-cell and closed-cell composite structures, and penetrating capillary micro-tubes can be seen in the foaming beads, so that the secondary forming is free from collapse. Under the condition that other process conditions are not changed, the expansion ratio of the expanded beads can be effectively adjusted to be about 1-15 times by changing the conditions of process water pressure, temperature and the like.
Example 10
Compared with example 6, the modified polymer material is mostly the same except that the modified polymer material in this example is polyester type thermoplastic polyurethane elastomer.
The TPEE foamed bead prepared by the embodiment has an obvious open-cell and closed-cell composite structure, excellent elastic recovery performance during kneading, and no collapse during secondary molding. In addition, the expansion ratio range of the expandable beads which can be adjusted by adjusting the conditions such as the melting temperature and the temperature of the process water can be increased to about 1 to 15 times. And the foamed article obtained is substantially free from the problem of skin puncture even at a high expansion ratio of 10 to 15 times.
Example 11
Compared with the embodiment 6, the modified polyamide is mostly the same, except that the modified polymer material in the embodiment is a mixture of amide 6, polyamide 9, polyamide 10, polyamide 11 and polyamide 12 in a mass ratio of 1:1:1:1: 1.
The TPEE foaming beads modified by different nylon materials prepared by the embodiment all have obvious open-cell and closed-cell composite structures, and penetrating capillary micro-tubes can be seen in the foaming beads, so that the secondary forming is free from collapse. Under the condition that other process conditions are not changed, the expansion ratio of the expanded beads can be effectively adjusted to be about 1-15 times by changing the conditions of process water pressure, temperature and the like.
Example 12
Compared with example 6, the modified styrene-butadiene copolymer.
The TPEE foaming beads modified by different materials prepared by the embodiment all have obvious open-cell and closed-cell composite structures, and do not collapse after secondary molding. Under the condition that other process conditions are not changed, the expansion ratio of the expanded beads can be effectively adjusted to be about 1-12 times by changing the conditions of process water pressure, temperature and the like.
In this embodiment, the modified polymer material may be replaced by one or a combination of more of nylon elastomer, low-melting point copolymerized nylon, polyether thermoplastic polyurethane elastomer, polyester thermoplastic polyurethane elastomer, thermoplastic styrene-butadiene hydrogenated copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester, PBAT, PTT, PET, or the like.
Example 13
Compared with the embodiment 6, most of the materials are the same, except that 5 parts of a cross-linking agent is added in the embodiment, and the cross-linking agent is selected from a polyisocyanate group-containing polymer (specifically, a polyurethane polymer with an unblocked NCO content of 4-10%, or biuret polyisocyanate, or polyphenyl methane polyisocyanate, etc.).
Compared with the expanded beads in example 6, the expanded beads prepared in the embodiment have tensile strength improved by about 3-4MPa (test standard ISO527), tear strength improved by about 10-20% and elastic recovery performance improved by about 20-30%.
Example 14
Compared with example 6, the same is mostly true, except that 2 parts of a cross-linking agent is added in the example, and the cross-linking agent is selected from a polyepoxy group-containing polymer (specifically, ADR4370 of Basff, or a 4-functionality cycloaliphatic epoxy resin EPOLEAD 401 of Japan, and the like).
Compared with the expanded beads in example 6, the expanded beads prepared in the embodiment have tensile strength improved by about 2-3MPa (test standard ISO527), tear strength improved by about 15-20% and elastic recovery performance improved by about 15-25%.
Example 15
Compared with example 6, most of the same, except that 3 parts of cross-linking agent is added in the example, the cross-linking agent is selected from polymers containing polyhydroxy groups (specifically, Lianded TMP, or lacellol PLACCEL 300, or lacellol PLACCEL 400, etc. can be selected).
Compared with the expanded beads in example 6, the expanded beads prepared in the embodiment have tensile strength improved by about 3-4MPa (test standard ISO527), tear strength improved by about 15-20% and elastic recovery performance improved by about 22-30%.
Example 16
Compared with the embodiment 6, most of the same, except that 5 parts of cross-linking agent is added in the embodiment, the cross-linking agent is selected from polymer containing multi-carboxyl group (specifically, coordination polymer of 2,2,3, 3-azobenzene tetracid and metal ion, etc.).
Compared with the expanded beads in example 6, the expanded beads prepared in the embodiment have tensile strength improved by about 4-5MPa (test standard ISO527), tear strength improved by about 15-20% and elastic recovery performance improved by about 20-30%.
Example 17
Most of them are the same as in example 1, except that in this example 50 parts of a crosslinking agent are added, which is a mixture of a polyisocyanate group-containing polymer (MDI, or a copolymer of MDI and a polyether polyol having NCO groups at both ends) and a polyol group-containing polymer (polyether polyol, etc.) in a molar ratio of 1.2: 1.
Compared with the expanded bead of example 1, the expanded bead of the present example has more dense cells, the expansion ratio can be increased to about 6 to 12 times, and the tear strength is increased by about 50% or more.
Examples 18 to 26
Compared with example 6, most of the materials are the same, except that the modified polymer material is respectively and independently selected from nylon elastomer, low-melting point copolymerized nylon, maleic anhydride grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester, PBAT, PTT or PET.
Similarly to example 6, expanded beads having a composite of a distinct open-cell structure and a closed-cell structure were also finally prepared. The foaming ratio can be controlled to be about 1-12 times or even wider by changing the process water pressure and the temperature.
Example 27
In each of the above embodiments 1 to 26, in this embodiment, 0.5 to 1.5 parts of an auxiliary functional additive may be selected, and the auxiliary functional additive may be one or more selected from antioxidants (antioxidant 1010, antioxidant 1135, antioxidant 1098, DLTP, etc.), UV absorbers (UV327, UV328, UV329, etc.), hydrolysis resistant carbodiimide, lubricant or release agent polyamide wax, oxidized polyethylene wax, oxidized polypropylene wax, etc., according to the requirements of the foam material.
Finally, the expanded beads with obvious open-cell structures and closed-cell structures are prepared in the same way. The foaming ratio can be controlled to be about 1-12 times or even wider by changing the process water pressure and the temperature.
Example 28
Different from the embodiment 1, the preparation method adopts a mould to shape and foam, and comprises the following specific steps:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder together, so that the material is hot-melted under the action of high-temperature high-pressure high-mechanical shearing force, and the TPEE and other materials are fully homogenized through a screw;
(2): and (2) injecting a foaming agent into the mixture homogenized in the step (1), continuously homogenizing, pushing the TPEE melt containing the foaming agent and other additives into a melt pump through a screw, controlling the inlet pressure of the melt pump to be 10Mpa, regulating the rotating speed of the melt pump and the like to stabilize the melt pressure in the double-screw extruder to be 100bar, and finely regulating the temperature of the melt entering the melt pump to be 180 ℃ from the double-screw extruder, the rotating speed of the screw and the like.
(3): the TPEE mixed hot melt is forcibly conveyed to the die head by the melt pump and is extruded into the shaping die by the die head, the shaping die is equipment which can simultaneously control pressure and temperature, the melt containing foaming gas nuclei is controlled to expand under a proper condition, and the cooling temperature or the cooling rate of the die is controlled according to the viscosity of the melt and the melting temperature or the crystallization temperature of the material, so that the foaming melt is uniformly cooled, the foaming melt is prevented from skinning too fast to reach a proper foaming ratio or being punctured by gas with volume expansion, generally speaking, the surface temperature of the shaping die is 100 ℃, and the pressure is (0.5-5 Mpa).
Similarly to example 6, expanded beads having a composite of a distinct open-cell structure and a closed-cell structure were also finally prepared. The foaming ratio can be controlled to be about 1-15 times or even wider by changing the process water pressure and temperature.
Example 29
Unlike example 28, in this example, the surface temperature of the forming mold was controlled to 70 ℃ and the pressure was controlled to 0.8 to 3.5 MPa.
Similarly to example 6, expanded beads having a composite of a distinct open-cell structure and a closed-cell structure were also finally prepared. The foaming ratio can be controlled to be about 1-15 times or even wider by changing the process water pressure and temperature.
The foamed materials obtained in the above examples 28 and 29 can be shaped like a plate or other irregular member according to the shape of the forming mold, and the above process for preparing the forming mold is also applicable to all the above examples.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. The thermoplastic polyether ester elastomer foam material is characterized by being prepared from the following raw materials in parts by weight: 50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material,0.05-2 parts of nucleating agent and 0.1-5 parts of foaming agent, and when the addition amount of the modified polymer material is 0, the melting temperature T of the polyether ester TPEE is2And Vicat softening point temperature T1Difference value T of2-T1The elongation at break is more than or equal to 30 ℃, and the tensile strength is more than or equal to 15 MPa;
the modified polymer material is selected from one or a combination of more of polyamide 6, polyamide 9, polyamide 10, polyamide 11, polyamide 12, low-melting-point copolymerized nylon, thermoplastic styrene-butadiene hydrogenated copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting-point polyester, PBAT, PTT or PET.
2. The thermoplastic polyether ester elastomer foam material as claimed in claim 1, wherein the nucleating agent is one or more of modified nano calcium carbonate, 2-10 μm talcum powder, modified montmorillonite, silicon dioxide and PMMA powder;
the foaming agent is one or a combination of more of Freon, n-butane, n-pentane, isopentane, carbon dioxide or nitrogen.
3. The thermoplastic polyether ester elastomer foam material as claimed in claim 1, wherein the cross-linking agent is added in an amount not more than 50 parts.
4. The thermoplastic polyether ester elastomer foam material as claimed in claim 3, wherein the cross-linking agent is one or more of a polymer containing polyisocyanate groups, a polymer containing polyepoxy groups, a polymer containing polyhydroxy groups or a polymer containing polycarboxyl groups.
5. The thermoplastic polyether ester elastomer foam material as claimed in claim 4, wherein the crosslinking agent is a mixture of a polymer containing polyisocyanate groups and a polymer containing polyhydroxy groups.
6. The method for preparing the thermoplastic polyether ester elastomer foam material as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
(1): adding the polyether ester TPEE and other raw material components except the foaming agent into a double-screw extruder, and fully melting and homogenizing;
(2): injecting a foaming agent into the homogenized mixture obtained in the step (1), and continuously homogenizing to obtain a homogenized melt;
(3): and extruding the homogenized melt into a melt pump, conveying the melt into a die head, extruding and foaming to obtain the foaming material.
7. The process for producing a thermoplastic polyether ester elastomer foam material as claimed in claim 6, wherein in the step (1), the polyether ester TPEE and other raw material components except the blowing agent are heated and melted in a twin-screw extruder under the conditions that: the heating temperature is within the temperature range of +/-50 ℃ of the melting temperature of the polyether ester TPEE;
in the step (2), the melt pressure of the material mixing area after the foaming agent is added into the double-screw extruder is 20 bar-200 bar;
in the step (3), the temperature of the homogenized melt extruded into the melt pump is 140-240 ℃, and the pressure is 0.2-20 MPa.
8. The process for preparing a thermoplastic polyetherester elastomer foam according to claim 6, wherein the internal structural arrangement in the twin-screw extruder ensures: in the extrusion process, the screw extrusion molding mixing area after the foaming agent is added and the screw extrusion molding mixing area before the foaming agent is added are sealed and backflow is stopped.
9. The method for preparing the thermoplastic polyether ester elastomer foam material as claimed in claim 6, wherein the melt of the extrusion die head directly enters the underwater pelletizing chamber for foaming, the pressure in the underwater pelletizing chamber is 0.1-1.2Mpa, and the temperature of the process cooling water is 40-100 ℃;
and directly feeding the melt of the extrusion die head into a shaping die for foaming, wherein the surface temperature of the shaping die is 30-100 ℃, and the pressure is 0.5-5 MPa.
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