CN108864662A - A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof - Google Patents
A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof Download PDFInfo
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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
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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
- C08J9/14—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
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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- 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
Abstract
The present invention relates to a kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof, the foam material is made of the raw material components of following parts by weight：50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material, 0.05-2 parts of nucleating agent, 0.1-5 parts of foaming agent, and when modified polymer material additive amount is 0, the melting temperature T of the polyether ester TPEE2With vicat softening point temperature T1Difference T2‑T1≥30℃.Compared with prior art, the invention proposes the formula that can be continuous foamed of TPEE and continuous foamed techniques, solve existing TPEE and are difficult to that the foamed material of stability is made, are especially difficult to continuous foamed problem.
Description
Technical field
The invention belongs to high molecular foam material technical fields, are related to a kind of elastomer foamed material of thermoplastic polyether ester TPEE
Expect preparation method.
Background technique
Thermoplastic polymer elastic material is widely used in all kinds of productions and living facilities, equipment, tool and consumables
On, the requirement with the development of society to environmental protection, energy conservation, consumption reduction etc., the demand of material lightweight also becomes increasingly tighter
Compel.Thermoplastic polymer elastic material also largely starts light-weighted experiment and verifies and continue to promote and apply.For example, polypropylene
PP foaming, polythene PE foaming, polystyrene PS foaming, polyester PET foaming, polyamide PA foaming and polyurethane TPU foaming etc..
The melt strength of thermoplastic polyether ester elastomer TPEE is low, and melt epidermis polyester portion crystallization when discharge expands is fast, polyethers portion
Divide and generate cracking gas leakage, significantly impacts the Bulking Time of polyether ester TPEE, so that expansion ratio and foam structure are affected, into
And the application of TPEE foamed material is limited, so that existing TPEE can only generally be carried out using techniques such as autoclave foaming.
Currently, autoclave foaming has the following disadvantages：1) kettle volume is foamed greatly again in high temperature >=120 DEG C, high pressure is greater than etc.
In 12Mpa, process safety condition is poor.2) low efficiency, since the molecular structure of TPEE causes physical blowing agent permeability low, so
Elastomer residence time in foaming kettle is long.3) yield is low, and during discharge, the vortex of explosion relief is acted on so that in kettle
Pressure drop rate on each point is seriously different, causes the expansion ratio of material widely different, the material of close expansion ratio
Only account for the 50~80% of total amount.4) process line of autoclave foaming limits that the technique is had no idea or means are to foamed material
Outer wall and inner core carry out temperature differentiated adjustment, so material is practically in soft state or elastomeric state rather than viscous state in kettle
Or molten condition, the outer wall of such material are the nuclei of bubbles of continuous phase package inner core, foam structure also can not just be needed according to market
It asks and is adjusted, foaming body can only be fully closed pore structure, and the foamed material of single fully closed pore structure is in downstream application approach
It will become very narrow.
But TPEE material has many physical property advantages again, as it is with high-wear resistance, more high heat resistance, high stretching die
Amount and compression modulus, excellent fatigue performance etc., so that it is with very big application prospect.Therefore, if one kind can be provided
The continuous foamed technique such as the extruded plastic foam of TPEE and casting foaming, the low efficiency for overcoming traditional autoclave to foam, expanded particle grain
Diameter is uneven, foam structure is difficult to the problem of adjusting, and can must greatly widen the application range of TPEE foamed material.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of thermoplastic polyether esters
Elastomer foamed material and preparation method thereof, specifically propose TPEE formula that can be continuous foamed and continuous foamed technique,
It solves existing TPEE to be difficult to that the foamed material of stability is made, is especially difficult to continuous foamed problem.
The purpose of the present invention can be achieved through the following technical solutions：
The invention proposes a kind of thermoplastic polyether ester elastomer foamed materials, using the raw material components of following parts by weight
It is made：50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material, 0.05-2 parts of nucleating agent, 0.1-5 parts of foaming agent, and
When modified polymer material additive amount is 0, the melting temperature T of the polyether ester TPEE2(testing standard ISO11357) with
Vicat softening point temperature T1The difference T of (testing standard ISO 306)2-T1≥30℃。
Further, elongation at break (testing standard ISO527) >=300% of polyether ester TPEE, in above-mentioned physical property condition
Polyether ester TPEE selection under, the additive amount of modified polymer material can be zero.Preferably, tensile strength (testing standard ISO
527) >=15Mpa, in this manner it is ensured that material is when discharge foams, melt will not be high (when especially expansion ratio >=4 times)
The gas core of speed expansion all punctures, and the tensile strength of material also available guarantee after foaming, about >=1N/mm2 (GB/
T528).It meanwhile being to guarantee that mobility and extensibility of the material in viscous state could be wrapped up to the limitation of elongation at break
Firmly more gas cores, to meet foaming demand.And T2-T1At >=30 DEG C, melt has enough humidity provinces in the case where forcing cooling
Between, make gas core foaming (i.e. melt swell) and cooling and shaping (i.e. abscess steep that wall skinning is formed) there is time enough difference to ensure technique
Operability.
When polyether ester TPEE is using conventional common product, when physical property is not within the scope of above-mentioned limit standard, modified poly
The additive amount of object material is not zero, and preferably 1-50 parts or so.
In a preferred embodiment of the invention, the modified polymer material selects polyamide 6, polyamide
9, polyamide 10, polyamide 11, polyamide 12, nylon elastomer, low melting point copolymer nylon, polyether thermoplastic elastic polyurethane
Body, polyester-type thermoplastic polyurethane elastomer, thermoplastic styrene-butadiene hydrogenation copolymer, maleic anhydride-g-SBS, horse
One of maleic anhydride grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester, PBAT, PTT or PET etc. or
A variety of combinations.
In above-mentioned difference modified polymer material, polyamide 6 I, polyamide 9, polyamide 10, polyamide 11, polyamide 12
Deng other nylon crystallinity are low or the material of unformed class has following advantage when modified：1) the regular crystalline region of TPEE is destroyed,
The crystallization temperature for reducing intermingling material, skinning speed will not be too fast when keeping physical blowing agent readily permeable and melt cooling, have
Foaming and setting in foaming and setting or mold is cut with underwater conducive to extrusion molding is continuous foamed；2) modified material is because of the portion between TPEE
Split-phase capacitive, so can be convenient gas core there are phase boundary and phase gap when being blended and enter at phase boundary, and then design special edge
The air flue in phase boundary and phase gap changes foam structure.
Polyester or polyether thermoplastic polyurethane have following advantage when modified：1) improve TPEE melt intensity,
Ensure that melt will not be punctured by gas core completely when foaming, when especially for obtaining higher expansion ratio, when improving melt
After temperature and pelletizing coolant-temperature gage, without very high melt strength, foamed material brokenly bubble rate can be very high；2) rule for destroying TPEE is brilliant
Area reduces the crystallization temperature of intermingling material, and skinning speed will not be too fast when keeping physical blowing agent readily permeable and melt cooling.
It is continuous foamed and cut foaming and setting in foaming and setting or mold under water to be conducive to extrusion molding.
The modification advantage of Maleated SEBS, graft rubber and the olefin elastomer containing polar side chain etc.：1) rubber being grafted
Or polyolefin and rubber containing polar side chain and elastomer are mostly amorphous state or hypocrystalline or not crystalline high polymer, it can be with
The continuous phase of TPEE and the continuity of hard section are destroyed, improve modified melt still can maintain melt sufficient intensity at high temperature；
2) because TPEE and rubber polymer can only partially compatible, phase boundary is obvious, and the permeability of foaming agent also differs greatly, can
To design suitable foam structure and opening and closing hole ratio.
In a preferred embodiment of the invention, the nucleating agent is modified nano calcium carbonate, 2~10 μm
It is one or more of in talcum powder, modified montmorillonoid, silica and PMMA powder
Further, foaming agent is 0.1-2 parts preferred.Further, nucleating agent preferably 0.1~0.5%.
In a preferred embodiment of the invention, the foaming agent be freon, it is normal butane, pentane, different
The combination of one or more of pentane, carbon dioxide or nitrogen.
In a preferred embodiment of the invention, the crosslinking no more than 50 parts is additionally added in composition of raw materials
Agent.It is furthermore preferred that the crosslinking agent is containing polyisocyanate-based polymer, the object of radical polymerisation containing multi-epoxy, base containing polyhydroxy
Group's polymer or the combination containing one or more of more carboxylic group polymer.The addition of crosslinking agent can allow the molecule of TPEE
Crosslinking points are generated between chain, so that the physical property of material is for example after the melt strength and foaming under improving high temperature：Tensile strength,
Tearing strength, elasticity recovery etc..
Even more preferably, the crosslinking agent is containing polyisocyanate-based polymer and radical polymerisation containing polyhydroxy
The mixing of object.At this point, expanded bead tearing strength obtained can significantly improve about 50% or more.
Further, the physical property requirement of the thermoplastic polyether ester elastomer foamed material prepared as needed, the present invention is also
Additional functionality auxiliary agent can be added in formula, such as antioxidant (antioxidant 1010, antioxidant 1135, antioxidant 1098, DLTP
Deng), UV absorbent (UV327, UV328, UV329 etc.), hydrolysis agent carbodiimides, lubricant or release agent polyamide wax,
Oxidized polyethylene wax, the one of the above such as chlorinated polypropylene wax or several, additive amount are 0.1-10 parts or so, preferably 0.5-1.5 parts.
The second object of the present invention is to propose the thermoplastic polyether ester elastomer foamed material of one of above-mentioned purpose
Preparation method includes the following steps：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added to Bitruder together
In, melting is abundant and is homogenized；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, obtains the melt that homogenizes；
(3)：The gained melt that homogenizes then is squeezed into Melt Pump, is then delivered to die head, is squeezed out, and is foamed to get arriving
Foamed material.
In a preferred embodiment of the invention, in step (1), polyether ester TPEE is heated in Bitruder
With other raw material components other than foaming agent and melt condition be：Heating temperature is in melting temperature ± 50 DEG C of polyether ester TPEE
Within the temperature range of.When extrusion temperature is lower than melting temperature, material is in the elastomeric state of softening point or more, at this point, in screw rod
Strong shear under, each material can also homogenize, in addition, screw rod heating temperature does not represent melt temperature, also need to consider spiral shell here
The shearing force bring of bar heats effect.
In a preferred embodiment of the invention, in step (2), after foaming agent is added in Bitruder
The melt pressure of material Mixed Zone is 20bar~200bar.Melt pressure is exactly the pressure of the specific region in extruding machine,
Corresponding melt temperature needs corresponding melt pressure to ensure that physical blowing agent can penetrate into the shorter time
It is wrapped inside melt and by melt.Melt pressure is excessively high, and to mean that foaming agent penetrates more, and at high temperature, foaming agent just becomes
The plasticiser of melt, melt strength can decline very big.Melt pressure is too low, and foaming agent is unable to ensure enough infiltrations in extruding machine
Saturating rate, to influence foaming effect.
In a preferred embodiment of the invention, in step (3), it is squeezed into the melt that homogenizes in Melt Pump
Temperature is 140~240 DEG C, pressure 0.2-20Mpa.
In a preferred embodiment of the invention, internal structure setting guarantees in Bitruder：It squeezed out
Cheng Zhong, the screw extrusion Mixed Zone sealing before screw extrusion Mixed Zone and addition foaming agent and non-return after foaming agent is added
Stream.
In a preferred embodiment of the invention, the melt of extrusion die is directly entered in underwater cutpellet room and sends out
Bubble, the indoor pressure of underwater cutpellet are 0.1-1.2Mpa, and the temperature of process cooling water is 40-100 DEG C.At this point, as low-pressure side
The pressure of underwater cutpellet room and the temperature of process cooling water need to guarantee there is enough pressure and temperature difference with die head high-pressure side.It is molten
Discharge speed when the pressure of body and the pressure difference of underwater cutpellet room will affect foaming is to influence cell size and density, temperature
Difference is construed as the water temperature difference of melt temperature and underwater cutpellet room, i.e., temperature difference size affects the melt skinning time and steep that wall is fixed
Type time and abscess expansive time.
In a preferred embodiment of the invention, the melt of extrusion die is directly entered foaming in shaper,
Shaper surface temperature is 30-100 DEG C, and pressure is 0.5~5Mpa, preferably 0.8~3.5Mpa.
Compared with prior art, the invention has the characteristics that：
(1) since the high crystallization temperature of polyether ester TPEE and nucleus shaping speed cause in the world without successful extruding machine
Filling physical blowing agent and the case that TPEE expanded bead particle is made in pelletizing technique under water, the present invention can be squeezed by limiting
The polyether ester TPEE key physical data (such as melting temperature) for moulding foaming, being required by the physical property of typing of the present invention can be from commercially available
Raw material is selected in TPEE type to ensure being suitable for extruded plastic foam technique, or is obtained by material modification and met typing pass of the present invention
Key physical property material obtains the TPEE copolymer of suitable extruded plastic foam technique.
(2) by control melt in the on high-tension side pressure of die head (i.e. Melting pump side) and in the melt pressure of die head low-pressure side
Power (i.e. die head and underwater cutpellet room or shaper contact side) come ensure the discharge speed of material to control cell size,
It is unlikely to pressure difference and crosses that atmosphere swelling of nucleus is too fast to be caused breakdown before melt prepattern, obtains having large scale inside outer surface or particle
Brokenly bubble or puncture the particle in duct, be also unlikely to the excessively stingy core of pressure difference and have little time expansion sufficiently just cooling and shaping.
(3) pelletizing water in intermingling material melting temperature ± 50 DEG C and while being controlled by the temperature of melt in control extruding machine
The pelletizing coolant-temperature gage of room is at 40-100 DEG C, and preferably 60~80 DEG C, so as to be precisely controlled the cooling and shaping time of expanded beads,
To obtain excellent shape and suitable particle size.
(4) or by control melt in the on high-tension side pressure of die head and mold runner pressure (i.e. die head low-pressure side) come it is true
The discharge speed of material is protected to controlling cell size, is unlikely to pressure difference and crosses that atmosphere swelling of nucleus is too fast to lead to the big face in melt outer surface
Product is breakdown, is also unlikely to the excessively stingy core of pressure difference and has little time expansion sufficiently just cooling and shaping, makes finished product outer dimension and design
Size difference is excessive.
(5) or by the temperature of melt in control extruding machine in intermingling material melting temperature ± 50 DEG C and while mold is controlled
Each surface temperature is at 30~100 DEG C, so as to be precisely controlled the cooling and shaping time of expanded beads, to obtain qualified system
Product surface and size.
(6) it by the process combination of multistage twin-screw and multistage Melt Pump and dynamic static mixer etc., can be adjusted flexibly
Material applicable row in process and versatility are also able to achieve the modular combination of technique, to realize TPEE in common process
Foam limitation problem in environment.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.The present embodiment is based on the technical solution of the present invention
Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
A kind of thermoplastic polyether ester elastomer foamed material, wherein necessary raw material group becomes：80 parts of polyether ester TPEE, at
0.5 part of core agent, 1.5 parts of foaming agent.Wherein, the melting temperature T of polyether ester TPEE2(testing standard ISO11357) and dimension card softening
Point temperature T1The difference T of (testing standard ISO 306)2-T1=75 DEG C, tensile strength (testing standard ISO 527)=25Mpa, break
It splits elongation (testing standard ISO527) and is approximately equal to 850%, nucleating agent is modified nano calcium carbonate, and foaming agent is carbon dioxide.
The present embodiment preferably uses underwater cutpellet foaming to prepare foamed material, and detailed process is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
Controlled at material melt temp, so that material heats under the high mechanical shear stress effect of high temperature and pressure, it will by screw rod
TPEE and other materials homogenizing are abundant；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed etc. in 10Mpa
To stablize melt pressure in Bitruder, in 100bar, melt enters the temperature of Melt Pump by Bitruder and screw rod
Revolving speed etc. is fine-tuning to 180 DEG C.
(3)：TPEE heat of mixing melt conveying is entered pelletizing water chamber, TPEE to die head, and by die head by force by Melt Pump
Melt in pelletizing water chamber by underwater pelletizer THE ADIABATIC SHEAR IN at melt bead particles, the pressure control in pelletizing water chamber exists
0.6Mpa, melt enter the low-pressure side of contact pelletizing water chamber in the high-pressure side (contacting side, 10Mpa with Melt Pump) of die head
(0.6Mpa) within 0.01~1 second time, is being cut due to discharge by the gas core that the melt that grain-cutter is cut into bead is wrapped up
It expands rapidly in grain water chamber and pelletizing water pipeline and is cooled down rapidly by pelletizing water.The expansion process can pass through the length of pelletizing water pipeline
Degree and diameter and booster pump control, and pelletizing water pressure is in 0.6Mpa, while by pelletizing water water tank heater and pelletizing water
Cooler etc. carrys out accurate adjustment cooling technique coolant-temperature gage at 70 DEG C, to adjust Beads cooling time to obtain suitable TPEE pearl
The expansion ratio of grain.
Thermoplastic polyether ester elastomer foamed material in the present embodiment can also prepare work using remaining conventional extruding
It is prepared by skill.
Comparative example 1
Compared with Example 1, the overwhelming majority is all identical, in addition to polyether ester TPEE uses general commercial product, (please supplement it
Concrete model), measure its melting temperature T2(testing standard ISO11357) and vicat softening point temperature T1(testing standard ISO
306) difference T2-T1=20 DEG C.
Comparative example 2
Compared with Example 1, the overwhelming majority is all identical, in addition to the fracture of polyether ester TPEE employed in the present embodiment is stretched
Long rate is about 150% or so.
Comparative example 3
Compared with Example 1, the overwhelming majority is all identical, in addition to melt pressure is changed in Bitruder in the present embodiment
Control is in 10bar.
Comparative example 4
Compared with Example 1, the overwhelming majority it is all identical, in addition in Bitruder melt pressure be changed to control exist
250bar。
Foamed material made from above-described embodiment and comparative example is observed and detects, concrete outcome is referring to the following table 1.
The performance of TPEE foamed material made from each embodiment of table 1
The present invention is by respectively to the melting temperature of TPEE it can be seen from above embodiments 1 and the data of comparative example 1-5
Be defined with physical property such as the poor, elongation at break of vicat softening point temperature, last obtained foaming product expandable operability,
Expandable multiplying power or foaming product molding etc. increase, and then respectively from it is one-sided or it is many-sided be improved, solve
Existing TPEE expanded beads of having determined are difficult to realize continuous foamed problem.
Embodiment 2
A kind of thermoplastic polyether ester elastomer foamed material, wherein necessary raw material group becomes：50 parts of polyether ester TPEE, at
0.05 part of core agent, 0.1 part of foaming agent.Wherein, the melting temperature T of polyether ester TPEE2(testing standard ISO11357) and dimension card are soft
Change point temperature T1The difference T of (testing standard ISO 306)2-T1About 30 DEG C, tensile strength (testing standard ISO 527) is about
30Mpa, elongation at break (testing standard ISO527) are about 600%, and nucleating agent is the talcum powder of 2~10um, and foaming agent is nitrogen
Gas.
The present embodiment prepares foamed material using underwater cutpellet foaming, and detailed process is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
So that material heats under the high mechanical shear stress effect of high temperature and pressure, TPEE and other materials are homogenized sufficiently by screw rod；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed in 0.2Mpa
Etc. stablizing in Bitruder melt pressure in 20bar, melt enter the temperature in Melt Pump by Bitruder and
Screw speed etc. is fine-tuning to 210 DEG C.
(3)：TPEE heat of mixing melt conveying is entered pelletizing water chamber, TPEE to die head, and by die head by force by Melt Pump
Melt in pelletizing water chamber by underwater pelletizer THE ADIABATIC SHEAR IN at melt bead particles, the pressure control in pelletizing water chamber exists
0.1Mpa, melt enter the low-pressure side of contact pelletizing water chamber in the high-pressure side (contacting side, 0.2Mpa with Melt Pump) of die head
(0.1Mpa) within 0.01~1 second time, is being cut due to discharge by the gas core that the melt that grain-cutter is cut into bead is wrapped up
It expands rapidly in grain water chamber and pelletizing water pipeline and is cooled down rapidly by pelletizing water.The expansion process can pass through the length of pelletizing water pipeline
Degree and diameter and booster pump control, and pelletizing water pressure is in 0.1Mpa, while by pelletizing water water tank heater and pelletizing water
Cooler etc. carrys out accurate adjustment cooling technique coolant-temperature gage at 80 DEG C, to adjust Beads cooling time to obtain suitable TPEE pearl
The expansion ratio of grain.
TPEE expanded bead epidermis obtained by the present embodiment is continuous, and grain shape is stablized without collapsing, uniform particle sizes, foaming
Multiplying power is at 2-3 times or so, and post forming is without collapsing.After through change technique water pressure and temperature, adjustable granule foaming
Multiplying power scope is 1-7 times or so.
Embodiment 3
A kind of thermoplastic polyether ester elastomer foamed material, wherein necessary raw material group becomes：95 parts of polyether ester TPEE, at
0.1 part of core agent, 5 parts of foaming agent.Wherein, the melting temperature T of polyether ester TPEE2(testing standard ISO11357) and Vicat softening point
Temperature T1The difference T of (testing standard ISO 306)2-T1>=30 DEG C, tensile strength (testing standard ISO 527) >=15Mpa, fracture
Elongation (testing standard ISO527) >=300%, nucleating agent are modified montmorillonoid, and foaming agent is that carbon dioxide and nitrogen press volume
Than 1:1 mixing.
The present embodiment prepares foamed material using underwater cutpellet foaming, and detailed process is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
So that material heats under the high mechanical shear stress effect of high temperature and pressure, TPEE and other materials are homogenized sufficiently by screw rod；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed etc. in 20Mpa
To stablize melt pressure in Bitruder, in 200bar, melt enters the temperature in Melt Pump by Bitruder and spiral shell
Bar revolving speed etc. is fine-tuning to 230 DEG C.
(3)：TPEE heat of mixing melt conveying is entered pelletizing water chamber, TPEE to die head, and by die head by force by Melt Pump
Melt in pelletizing water chamber by underwater pelletizer THE ADIABATIC SHEAR IN at melt bead particles, the pressure control in pelletizing water chamber exists
1.2Mpa, melt enter the low-pressure side of contact pelletizing water chamber in the high-pressure side (contacting side, 20Mpa with Melt Pump) of die head
(1.2Mpa) within 0.01~1 second time, is being cut due to discharge by the gas core that the melt that grain-cutter is cut into bead is wrapped up
It expands rapidly in grain water chamber and pelletizing water pipeline and is cooled down rapidly by pelletizing water.The expansion process can pass through the length of pelletizing water pipeline
Degree and diameter and booster pump control, and pelletizing water pressure is in 1.2Mpa, while by pelletizing water water tank heater and pelletizing water
Cooler etc. carrys out accurate adjustment cooling technique coolant-temperature gage at 95 DEG C, to adjust Beads cooling time to obtain suitable TPEE pearl
The expansion ratio of grain.
TPEE expanded bead epidermis obtained by the present embodiment is continuous, and grain shape is stablized without collapsing, uniform particle sizes, foaming
Multiplying power is at 4-6 times or so, and post forming is without collapsing.After through change technique water pressure and temperature, adjustable granule foaming
Multiplying power scope is 1-8 times or so.
Embodiment 4
A kind of thermoplastic polyether ester elastomer foamed material, wherein necessary raw material group becomes：TPEE70 parts of 45D polyether ester,
0.2 part of nucleating agent, 0.5 part of foaming agent.Wherein, the melting temperature T of polyether ester TPEE2(testing standard ISO11357) and dimension card are soft
Change point temperature T1The difference T of (testing standard ISO 306)2-T1>=30 DEG C, tensile strength (testing standard ISO 527) >=15Mpa,
Elongation at break (testing standard ISO527) >=300%, nucleating agent are silica and modified montmorillonoid in mass ratio 1:1 it is mixed
It closes, foaming agent is butane and carbon dioxide according to volume ratio 1:1 mixing.
The present embodiment prepares foamed material using underwater cutpellet foaming, and detailed process is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
So that material heats under the high mechanical shear stress effect of high temperature and pressure, TPEE and other materials are homogenized sufficiently by screw rod；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed etc. in 5Mpa
To stablize melt pressure in Bitruder, in 80bar, melt enters the temperature in Melt Pump by Bitruder and spiral shell
Bar revolving speed etc. is fine-tuning to 220 DEG C.
(3)：TPEE heat of mixing melt conveying is entered pelletizing water chamber, TPEE to die head, and by die head by force by Melt Pump
Melt in pelletizing water chamber by underwater pelletizer THE ADIABATIC SHEAR IN at melt bead particles, the pressure control in pelletizing water chamber exists
0.3Mpa, melt enter the low-pressure side of contact pelletizing water chamber in the high-pressure side (contacting side, 8Mpa with Melt Pump) of die head
(0.3Mpa) within 0.01~1 second time, is being cut due to discharge by the gas core that the melt that grain-cutter is cut into bead is wrapped up
It expands rapidly in grain water chamber and pelletizing water pipeline and is cooled down rapidly by pelletizing water.The expansion process can pass through the length of pelletizing water pipeline
Degree and diameter and booster pump control, and pelletizing water pressure is in 0.3Mpa, while by pelletizing water water tank heater and pelletizing water
Cooler etc. carrys out accurate adjustment cooling technique coolant-temperature gage at 90 DEG C, to adjust Beads cooling time to obtain suitable TPEE pearl
The expansion ratio of grain.
TPEE expanded bead epidermis obtained by the present embodiment is continuous, and grain shape is stablized without collapsing, uniform particle sizes, foaming
Multiplying power is at 4-6 times or so, and post forming is without collapsing.After through change technique water pressure and temperature, adjustable granule foaming
Multiplying power scope is 1-12 times or so.
Embodiment 5
A kind of thermoplastic polyether ester elastomer foamed material, wherein necessary raw material group becomes：88 parts of polyether ester TPEE, at
2 parts of core agent, 2 parts of foaming agent.Wherein, the melting temperature T of polyether ester TPEE2(testing standard ISO11357) and Vicat softening point temperature
Spend T1The difference T of (testing standard ISO 306)2-T1>=30 DEG C, tensile strength (testing standard ISO 527) >=15Mpa, fracture is stretched
Long rate (testing standard ISO527) >=300%, nucleating agent are PMMA powder, and foaming agent is carbon dioxide.
The present embodiment prepares foamed material using underwater cutpellet foaming, and detailed process is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
So that material heats under the high mechanical shear stress effect of high temperature and pressure, TPEE and other materials are homogenized sufficiently by screw rod；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed etc. in 15Mpa
To stablize melt pressure in Bitruder, in 150bar, melt enters the temperature in Melt Pump by Bitruder and spiral shell
Bar revolving speed etc. is fine-tuning to 170 DEG C.
(3)：TPEE heat of mixing melt conveying is entered pelletizing water chamber, TPEE to die head, and by die head by force by Melt Pump
Melt in pelletizing water chamber by underwater pelletizer THE ADIABATIC SHEAR IN at melt bead particles, the pressure control in pelletizing water chamber exists
0.7Mpa, melt enter the low-pressure side of contact pelletizing water chamber in the high-pressure side (contacting side, 15Mpa with Melt Pump) of die head
(0.7Mpa) within 0.01~1 second time, is being cut due to discharge by the gas core that the melt that grain-cutter is cut into bead is wrapped up
It expands rapidly in grain water chamber and pelletizing water pipeline and is cooled down rapidly by pelletizing water.The expansion process can pass through the length of pelletizing water pipeline
Degree and diameter and booster pump control, and pelletizing water pressure is in 0.7Mpa, while by pelletizing water water tank heater and pelletizing water
Cooler etc. carrys out accurate adjustment cooling technique coolant-temperature gage at 60 DEG C, to adjust Beads cooling time to obtain suitable TPEE pearl
The expansion ratio of grain.
TPEE expanded bead epidermis obtained by the present embodiment is continuous, and grain shape is stablized without collapsing, uniform particle sizes, foaming
Multiplying power is at 6-7 times or so, and post forming is without collapsing.After through change technique water pressure and temperature, adjustable granule foaming
Multiplying power scope is 1-12 times or so.
Embodiment 6
Compared with Example 1, the overwhelming majority is identical, in addition to polyether ester TPEE uses conventional commercial substrate in the present embodiment,
Meanwhile 30 parts of modified polymer materials are also added into, the modified polymer material selects polyether thermoplastic polyurethane bullet
Property body.
TPEE expanded bead obtained by the present embodiment has apparent aperture and closed pore composite construction, expanded bead kneading
When elastic recovery properties it is excellent, post forming is without collapsing.In addition, by can after the adjusting conditions such as melting temperature and technique coolant-temperature gage
1-15 times or so can be increased to the expansion ratio range of expanded beads adjustment.And even if under 10-15 times of high foamability
Foaming product obtained also occurs without collapsing problem substantially.
Embodiment 7
Compared with Example 6, the overwhelming majority is identical, in addition to the additive amount of modified polymer material in the present embodiment is 50
Part.
Other than aperture is varied with volume ratio shared by hole-closing structure, the product properties and embodiment 6 of the present embodiment
It is essentially identical.
Embodiment 8
Compared with Example 6, the overwhelming majority is identical, in addition to the additive amount of modified polymer material in the present embodiment is 1 part.
TPEE expanded bead obtained by the present embodiment has apparent aperture and closed pore composite construction, expanded bead kneading
When elastic recovery properties it is excellent, post forming is without collapsing.In addition, by can after the adjusting conditions such as melting temperature and technique coolant-temperature gage
1-11 times or so can be increased to the expansion ratio range of expanded beads adjustment, post forming is without collapsing.And even if at 9-11 times
High foamability under foaming product obtained also occur substantially without collapsing problem.
Embodiment 9
Compared with Example 6, the overwhelming majority is identical, in addition to modified polymer material selects polyamide 6, poly- in the present embodiment
One of nylon materials such as amide 9, polyamide 10, polyamide 11, polyamide 12.
The various TPEE expanded beads modified using different nylon materials made from the present embodiment have obtained significantly opening
Hole and the compound structure of closed pore, and the visible perforative capillary micro-pipe in expanded bead, post forming is without collapsing.In remaining technique
In the constant situation of condition, the expansion ratio that expanded bead can be effectively adjusted by changing the conditions such as process water pressure and temperature exists
1-15 times or so.
Embodiment 10
Compared with Example 6, the overwhelming majority is identical, in addition to modified polymer material selects polyester-type thermoplastic in the present embodiment
Property polyurethane elastomer.
TPEE expanded bead obtained by the present embodiment has apparent aperture and closed pore composite construction, expanded bead kneading
When elastic recovery properties it is excellent, post forming is without collapsing.In addition, by can after the adjusting conditions such as melting temperature and technique coolant-temperature gage
1-15 times or so can be increased to the expansion ratio range of expanded beads adjustment.And even if under 10-15 times of high foamability
Foaming product obtained is also substantially without epidermis breakdown problem.
Embodiment 11
Compared with Example 6, the overwhelming majority is identical, in addition to modified polymer material selects amide 6, polyamides in the present embodiment
Amine 9, polyamide 10, polyamide 11 and polyamide 12 in mass ratio 1:1:1:1:1 mixing.
The various TPEE expanded beads modified using different nylon materials made from the present embodiment have obtained significantly opening
Hole and the compound structure of closed pore, and the visible perforative capillary micro-pipe in expanded bead, post forming is without collapsing.In remaining technique
In the constant situation of condition, the expansion ratio that expanded bead can be effectively adjusted by changing the conditions such as process water pressure and temperature exists
1-15 times or so.
Embodiment 12
Compared with Example 6, the overwhelming majority is identical, in addition to modified polymer material selects thermoplasticity benzene second in the present embodiment
Alkene-butadiene hydrogenation copolymer and maleic anhydride-g-SBS (mass ratio 1:1) mixing.
The various TPEE expanded beads modified using different materials made from the present embodiment obtained apparent aperture with
The compound structure of closed pore, post forming is without collapsing.In the constant situation of remaining process conditions, by changing technique water pressure and temperature
The conditions such as degree can effectively adjust the expansion ratio of expanded bead at 1-12 times or so.
In the present embodiment, above-mentioned modified polymer material may be replaced by nylon elastomer, low melting point copolymer nylon, gather
Ether type thermoplastic polyurethane elastomer, polyester-type thermoplastic polyurethane elastomer, thermoplastic styrene-butadiene hydrogenation copolymerization
Body, maleic anhydride-g-SBS, maleic anhydride grafting PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester,
One of PBAT, PTT or PET etc. or a variety of combinations.
Embodiment 13
Compared with Example 6, the overwhelming majority is identical, in addition to being also added into 5 parts of crosslinking agent in the present embodiment, crosslinking agent selection
Containing polyisocyanate-based polymer (concretely unclosed 4~10% polyether polyols of NCO content or biuret polyisocyanate
Cyanate or polyphenyl methane polyisocyanate etc.).
Compared to the expanded bead in embodiment 6, the tensile strength of expanded bead made from the present embodiment promotes about 3-
4Mpa or so (testing standard ISO 527), tearing strength improve about 10-20%, and elastic recovery properties improve about 20-30%.
Embodiment 14
Compared with Example 6, the overwhelming majority is identical, in addition to being also added into 2 parts of crosslinking agent in the present embodiment, crosslinking agent selection
The object of radical polymerisation containing multi-epoxy (ADR4370 of specific optional BASF, or 4 degree of functionality alicyclic epoxy tree of Japanese Daicel
Rouge EPOLEAD 401 etc.).
Compared to the expanded bead in embodiment 6, the tensile strength of expanded bead made from the present embodiment promotes about 2-
3Mpa or so (testing standard ISO 527), tearing strength improve about 15-20%, and elastic recovery properties improve about 15-25%.
Embodiment 15
Compared with Example 6, the overwhelming majority is identical, in addition to being also added into 3 parts of crosslinking agent in the present embodiment, crosslinking agent selection
The object of radical polymerisation containing polyhydroxy (specifically optional U.S. Li Ande TMP, or Japanese Daicel PLACCEL 300, or Japanese contest
Fine jade PLACCEL 400 etc.).
Compared to the expanded bead in embodiment 6, the tensile strength of expanded bead made from the present embodiment promotes about 3-
4Mpa or so (testing standard ISO 527), tearing strength improve about 15-20%, and elastic recovery properties improve about 22-30%.
Embodiment 16
Compared with Example 6, the overwhelming majority is identical, in addition to being also added into 5 parts of crosslinking agent in the present embodiment, crosslinking agent selection
Containing more carboxylic group polymer (specifically optional 2,2,3,3- azobenzene first tetracid and the coordination polymer of metal ion etc.).
Compared to the expanded bead in embodiment 6, the tensile strength of expanded bead made from the present embodiment promotes about 4-
5Mpa or so (testing standard ISO 527), tearing strength improve about 15-20%, and elastic recovery properties improve about 20-30%.
Embodiment 17
Compared with Example 1, the overwhelming majority is all identical, in addition to being also added into 50 parts of crosslinking agents in the present embodiment, uses
Containing polyisocyanate-based polymer (copolymer that the both ends that MDI or MDI and polyether polyol generate are blocked by NCO) and
The object of radical polymerisation containing polyhydroxy (polyether polyol etc.) in molar ratio 1.2:1 mixing.
Compared to the expanded bead of embodiment 1, the abscess of the expanded bead in the present embodiment is finer and close, and expansion ratio can increase
Greatly to 6-12 times or so, tearing strength increases about 50% or more.
Embodiment 18-26
Compared with Example 6, the overwhelming majority it is identical, in addition to modified polymer material individually select nylon elastomer,
Low melting point copolymer nylon, maleic anhydride are grafted PE, thermoplastic acrylic rubber, EVA elastomer, low-melting point polyester, PBAT, PTT
Or PET.
It is similar to Example 6, it has finally equally been prepared with obvious open-celled structure and the compound foaming of hole-closing structure
Bead.Expansion ratio can be even broader at 1-12 times or so by changing process water pressure and temperature control.
Embodiment 27
In the various embodiments described above 1-26, in the present embodiment, it is also an option that 0.5-1.5 parts of property additional functionality additive,
Additional functionality additive can need to select antioxidant (antioxidant 1010, antioxidant 1135, antioxidant according to foamed material
1098, DLTP etc.), UV absorbent (UV327, UV328, UV329 etc.), hydrolysis agent carbodiimides, lubricant or release agent
Polyamide wax, oxidized polyethylene wax, the one of the above such as chlorinated polypropylene wax or several.
Finally equally it has been prepared with obvious open-celled structure and the compound expanded bead of hole-closing structure.Expansion ratio can
It is even broader at 1-12 times or so by changing process water pressure and temperature control.
Embodiment 28
Different with embodiment 1, preparation method is foamed using mould shape, and specific step is as follows：
(1)：Other raw material components other than polyether ester TPEE and foaming agent are taken to be added in Bitruder together,
So that material heats under the high mechanical shear stress effect of high temperature and pressure, TPEE and other materials are homogenized sufficiently by screw rod；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, foaming agent will be contained by screw rod
It is pushed into Melt Pump with the TPEE melt of other auxiliary agents, control melt pump inlet pressure adjusts melt revolution speed etc. in 10Mpa
To stablize melt pressure in Bitruder, in 100bar, melt enters the temperature in Melt Pump by Bitruder and spiral shell
Bar revolving speed etc. is fine-tuning to 180 DEG C.
(3)：TPEE heat of mixing melt conveying is squeezed into shaper to die head, and by die head by force by Melt Pump,
Shaper is the equipment that pressure control and temperature control can have both simultaneously, controlled by the melt for controlling the gas core containing foaming under suitable conditions
Expansion, and control according to the melting temperature or crystallization temperature of the viscosity of melt and material mold cooling temperature or cooling rate from
And foamed melt is allowed uniformly to cool down, avoid foamed melt skinning from being unable to reach very much the too slow melt of suitable expansion ratio or skinning fastly
By the gas breakdown of volume expansion, it is however generally that, the surface temperature of shaper is 100 DEG C, and pressure is (0.5~5Mpa).
It is similar to Example 6, it has finally equally been prepared with obvious open-celled structure and the compound foaming of hole-closing structure
Bead.Expansion ratio can be even broader at 1-15 times or so by changing process water pressure and temperature control.
Embodiment 29
Different with embodiment 28, in the present embodiment, the surface temperature control of shaper is 70 DEG C, pressure control
It is made as (0.8~3.5Mpa).
It is similar to Example 6, it has finally equally been prepared with obvious open-celled structure and the compound foaming of hole-closing structure
Bead.Expansion ratio can be even broader at 1-15 times or so by changing process water pressure and temperature control.
Foamed material obtained by above-described embodiment 28 and embodiment 29 according to the shape of shaper can be plate-like or
Other shaped pieces, the preparation process of above-mentioned shaper are applied equally to all embodiments in front.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of thermoplastic polyether ester elastomer foamed material, which is characterized in that using the raw material components system of following parts by weight
At：50-95 parts of polyether ester TPEE, 0-50 parts of modified polymer material, 0.05-2 parts of nucleating agent, 0.1-5 parts of foaming agent, and work as
When modified polymer material additive amount is 0, the melting temperature T of the polyether ester TPEE2With vicat softening point temperature T1Difference
T2-T1≥30℃。
2. a kind of thermoplastic polyether ester elastomer foamed material according to claim 1, which is characterized in that the modification
Polymer material selects polyamide 6, polyamide 9, polyamide 10, polyamide 11, polyamide 12, nylon elastomer, low melting point total
Poly- nylon, Polyether-type thermoplastic polyurethane elastomer, polyester-type thermoplastic polyurethane elastomer, thermoplastic styrene-butadiene
It hydrogenates copolymer, maleic anhydride-g-SBS, maleic anhydride and is grafted PE, thermoplastic acrylic rubber, EVA elastomer, low melting point
One of polyester, PBAT, PTT or PET or a variety of combinations.
3. a kind of thermoplastic polyether ester elastomer foamed material according to claim 1, which is characterized in that the nucleation
Agent is one or more of in modified nano calcium carbonate, 2~10 μm of talcum powder, modified montmorillonoid, silica and PMMA powder；
The foaming agent is one or more of freon, normal butane, pentane, isopentane, carbon dioxide or nitrogen
Combination.
4. a kind of thermoplastic polyether ester elastomer foamed material according to claim 1, which is characterized in that its composition of raw materials
In be additionally added crosslinking agent no more than 50 parts.
5. a kind of thermoplastic polyether ester elastomer foamed material according to claim 4, which is characterized in that the crosslinking agent
For containing polyisocyanate-based polymer, the object of radical polymerisation containing multi-epoxy, the object of radical polymerisation containing polyhydroxy or contain more carboxylic groups
The combination of one or more of polymer.
6. a kind of thermoplastic polyether ester elastomer foamed material according to claim 5, which is characterized in that the crosslinking
Agent is the mixing containing polyisocyanate-based polymer and the object of radical polymerisation containing polyhydroxy.
7. the preparation method of the thermoplastic polyether ester elastomer foamed material as described in claim 1-6 is any, which is characterized in that
Include the following steps：
(1)：It takes other raw material components other than polyether ester TPEE and foaming agent to be added in Bitruder together, melts
Melt sufficiently and is homogenized；
(2)：Foaming agent is injected into the mixture after step (1) homogenizing again, continues to be homogenized, obtains the melt that homogenizes；
(3)：The gained melt that homogenizes then is squeezed into Melt Pump, is then delivered to die head, is squeezed out, and foaming is to get to foaming
Material.
8. the preparation method of thermoplastic polyether ester elastomer foamed material according to claim 7, which is characterized in that step
(1) polyether ester TPEE is heated in, in Bitruder and the condition of other raw material components other than foaming agent and melting is：Add
Hot temperature is within the temperature range of melting temperature ± 50 DEG C of polyether ester TPEE；
The melt pressure for the material Mixed Zone being added after foaming agent in step (2), in Bitruder be 20bar~
200bar；
In step (3), the temperature for being squeezed into the melt that homogenizes in Melt Pump is 140~240 DEG C, pressure 0.2-20Mpa.
9. the preparation method of thermoplastic polyether ester elastomer foamed material according to claim 7, which is characterized in that double spiral shells
Internal structure setting guarantees in bar extruding machine：In extrusion process, screw extrusion Mixed Zone and addition after foaming agent is added are sent out
The sealing of screw extrusion Mixed Zone and backflow before infusion.
10. the preparation method of thermoplastic polyether ester elastomer foamed material according to claim 7, which is characterized in that squeeze
The melt of die head is directly entered in underwater cutpellet room and foams out, and the indoor pressure of underwater cutpellet is 0.1-1.2Mpa, technical cooling
The temperature of water is 40-100 DEG C；
The melt of extrusion die is directly entered foaming in shaper, and shaper surface temperature is 30-100 DEG C, pressure 0.5
~5Mpa.
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