CN107177051A - The method for preparing thermoplastic elastomer foaming bead - Google Patents
The method for preparing thermoplastic elastomer foaming bead Download PDFInfo
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- CN107177051A CN107177051A CN201710413319.0A CN201710413319A CN107177051A CN 107177051 A CN107177051 A CN 107177051A CN 201710413319 A CN201710413319 A CN 201710413319A CN 107177051 A CN107177051 A CN 107177051A
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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
- 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
- C08J2203/08—Supercritical fluid
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a kind of method for preparing thermoplastic elastomer foaming bead, it is carbon dioxide and nitrogen mixed gas that this method, which can make inside expanded bead bubble, is shunk so as to suppress expanded bead bubble volume during air exchange, maintains larger expansion ratio.Methods described step impregnates including thermoplastic elastomer (TPE) bead in high pressure nitrogen atmosphere, and dipping temperature is normal temperature；The thermoplastic elastomer (TPE) bead for fully absorbing nitrogen is placed in supercritical carbon dioxide, progress is swelled diffusion, thermoplastic elastomer foaming bead is made in the thermoplastic elastomer (TPE) bead foam expansion of induction dissolving nitrogen and carbon dioxide.It is nitrogen and carbon dioxide gas mixture inside the thermoplastic elastomer foaming bead, during occurring gas exchanges with outside air under natural environment, due to the presence of nitrogen molecule in bubble, supports bubble structure, maintain higher product expansion ratio.
Description
Technical field
It is more particularly to a kind of to utilize cleaning foaming the present invention relates to a kind of method for preparing thermoplastic elastomer foaming bead
The method that gas prepares high magnification thermoplastic elastomer foaming bead.
Background technology
Thermoplastic elastomer (TPE) had both had the superior elasticity of rubber like, had the processing characteristics of general thermoplastic again.
A large amount of bubbles are imported in thermoplastic elastomer (TPE) matrix by physical blowing process, the thermoplastic elastomeric foaming material of formation,
It has a light weight, soft-touch, and elasticity is high, and permanent compression set is small, clean environment firendly, the features such as reusable edible, can be extensive
Applied to footwear material, sports goods, automotive trim, electronic device etc..
Thermoplastic elastomer foaming bead is initially formed by using physical blowing agent, then by steam molding in mould, made
Surface of beads welding forms foaming product, solves the problem of more difficult one step foaming of large scale foaming body is molded, is particularly conducive to
The large-scale production of thermoplastic elastomer foaming product with complex appearance structure.
It is environmentally harmful instead of CBA and inflammable using the foamed gas such as carbon dioxide or nitrogen of cleaning
Other physical blowing agents, make foaming product safe and harmless, foaming process clean environment firendly, neither influence environment, and can meet increasingly
Strict laws and regulations requirement, is the developing direction of macromolecule foaming.
Because nitrogen only has relatively low solubility and relatively low diffusion rate in the polymer, therefore use the foaming of nitrogen
Technique usually requires high nitrogen pressure, causes the high pressure resistant requirement to equipment higher, and because diffusion rate is slow, take compared with
It is long, cause production cost higher, therefore less be applied to bead foam.
Supercritical carbon dioxide has faster diffusion rate and higher solubility in thermoplastic elastomer (TPE), is often employed
In the bead foam of thermoplastic elastomer (TPE).Within the scope of the deformable temperature of thermoplastic elastic material, make overcritical titanium dioxide
Carbon dissolution is in thermoplastic elastomer (TPE) body, then by quick pressure releasing, triggers nucleation and the growth of bubble, forms thermoplastic elastic
Body expanded material.
For the thermoplastic elastomer foaming bead obtained using supercritical carbon dioxide foaming technique, just foaming is formed
It is entirely carbon dioxide in bubble.When it is placed in atmosphere, because nitrogen accounts for 78% in air, oxygen is accounted for
21%, cause the presence of the density of carbon dioxide gas gradient inside and outside bubble.Carbon dioxide, which can spread, escapes out expanded bead, and
Air can diffuse into bubble, until gas concentration and pressure balance inside and outside bubble.Due to carbon dioxide in the polymer
Diffusion rate much larger than the nitrogen of duty gas main component diffusion rate, when gas exchanges start inside and outside bubble, mainly with gas
Based on carbon dioxide is outwards escaped in bubble, occur air pressure in the state close to vacuum, bubble in bubble and be less than external air pressure
Stage, now static air pressure the thermoplastic expanded bead of flexibility can be made to occur significant volume contraction.As air is to bubble
Interior further diffusion, bubble inner pressure power is stepped up until external and internal pressure is equal, and bead volume can obtain part recovery, still
Its bubble volume is compared still to be reduced much when expansion is completed, and this process for first shrinking part recovery again, which turns into, to be limited
To the major reason compared with high foamability thermoplastic elastomeric foaming material.
The content of the invention
The present invention is existed in the prior art using the thermoplastic elastomer (TPE) of supercritical carbon dioxide foaming technique to overcome
With the volume contraction in outside air exchange process, the deficiency that expansion ratio reduces is caused to prepare thermoplastic elastomehc there is provided one kind
Property body expanded bead method, this method can make just foaming after expanded bead bubble inside be carbon dioxide and nitrogen mixture
Body, bubble structure is supported using nitrogen, maintains larger expansion ratio.
To achieve the above object, the present invention uses following technical scheme：
A kind of method for preparing thermoplastic elastomer foaming bead provided in an embodiment of the present invention, methods described includes：Nitrogen
Gas impregnation steps, thermoplastic elastomer (TPE) particle impregnates in high pressure nitrogen atmosphere, and dipping temperature is normal temperature, and acquisition fully absorbs nitrogen
The thermoplastic elastomer (TPE) particle of gas；Carbonic maceration step, the thermoplastic elastomer (TPE) particle for fully absorbing nitrogen is placed in super
In the carbon dioxide of critical condition, progress is swelled diffusion, obtains the thermoplastic elastomer (TPE) particle of dissolving nitrogen and carbon dioxide；It is swollen
The thermoplastic elastomer (TPE) particle foaming and intumescing of swollen step, induction dissolving nitrogen and carbon dioxide, is made thermoplastic elastomer foaming
It is nitrogen and carbon dioxide gas mixture inside bead, the thermoplastic elastomer foaming bead.
Preferably, the nitrogen impregnation steps further comprise：Thermoplastic elastomer (TPE) particle is in 5-60MPa high pressure nitrogens
Middle dipping, dipping temperature is normal temperature, and dip time is 2-20 hours, and nitrogen molecule is diffused into thermoplastic elastomer (TPE) particle,
Obtain the thermoplastic elastomer (TPE) particle for fully absorbing nitrogen.
Preferably, the carbonic maceration step further comprises, the thermoplastic elastomer (TPE) of nitrogen will be fully absorbed
Particle is placed in the closed vessel of blowing temperature, is passed through the supercritical carbon dioxide for meeting blow pressure, is swelled diffusion 5-
20 minutes, obtain the thermoplastic elastomer (TPE) particle of dissolving nitrogen and carbon dioxide.
Preferably, the blowing temperature, which is thermoplastic elastomer (TPE) particle, can occur plastic deformation, but can't flow
Temperature, for amorphous polymer, blowing temperature is within Tg~Tg+40 DEG C, and Tg is the glass transition of amorphous polymer
Temperature；For crystalline polymer, blowing temperature is within Tm-20 DEG C~Tm, and Tm is the fusing point of crystalline polymer.
Preferably, blowing temperature is 60 °~350 °.
Preferably, supercritical carbon dioxide pressure is 7~30MPa.
Preferably, the expansion step further comprises, the quick pressure releasing induction dissolving nitrogen and carbon dioxide
The nucleation of abscess and growth in thermoplastic elastomer (TPE) particle, are made thermoplastic elastomer foaming bead, the thermoplastic elastomer (TPE)
It is nitrogen and carbon dioxide gas mixture inside expanded bead.
Preferably, thermoplastic elastomer (TPE) particle is TPUE particle, block polyetheramides elastomer
Particle, polyolefin elastomer particle, thermoplastic polyester elastomer particle one of which or several combinations.
Preferably, the number-average molecular weight of thermoplastic elastomer (TPE) particle is 1~6,000,000.
Preferably, the particle diameter 0.5-10mm of thermoplastic elastomer (TPE) particle.
The present invention is improved existing supercritical carbon dioxide foaming technology, is soaked first by normal temperature high voltage nitrogen
Nitrogen molecule, is dissolved in inside thermoplastic elastomer (TPE) bead by stain before foaming, then again in the overcritical bar of HTHP
Carbon dioxide molecule is dissolved in inside thermoplastic elastomer (TPE) bead under part, by unexpected pressure release, induce nucleation and the life of abscess
It is long, prepare thermoplastic elastomer foaming bead.Described thermoplastic elastomer foaming bead foam complete when bubble inside be
Nitrogen and carbon dioxide gas mixture.
Described thermoplastic elastomer foaming bead is positioned in air after the completion of foaming, and bubble is inside and outside to occur gas friendship
Change, the carbon dioxide in bubble is outwards escaped.But nitrogen escape rate is low inside bubble and pressure is high, in gas exchange process
Being able to maintain that has enough air pressure inside bubble, to play a part of supporting bubble structure, can be prevented effectively from pure carbon dioxide
The low caused bubble volume contraction process of bubble internal pressure present in foam process, so as to maintain thermoplastic elastomer (TPE)
The higher expansion ratio of expanded bead.
Brief description of the drawings
Fig. 1 show the internal structure for the expanded bead that embodiment 1 is obtained.
Fig. 2 show the internal structure for the expanded bead that embodiment 4 is obtained.
Fig. 3 show the internal structure for the expanded bead that embodiment 7 is obtained.
Fig. 4 show the internal structure for the expanded bead that embodiment 10 is obtained.
Embodiment
The present invention is described further with reference to the accompanying drawings and detailed description.
Embodiment 1：It is 80,000 by 100g mean molecule quantities, average diameter is 3mm TPUE (TPU)
In autoclave under bead, input normal temperature and autoclave is sealed, open intake valve, be passed through nitrogen, make thermoplastic polyurethane bullet
Property body bead in 15MPa nitrogen atmosphere, normal temperature saturation impregnate 10 hours.
Nitrogen pressure in slow discharge kettle, opens autoclave, takes out the TPUE for having absorbed nitrogen
Bead, puts it into another autoclave for having reached 150 DEG C of blowing temperature of setting, autoclave is sealed, 10MPa is passed through
Supercritical carbon dioxide, pressurize 10 minutes.It is quick to open air bleeding valve, the carbon dioxide of autoclave is excluded, is caused
The nucleation of abscess and growth in TPUE matrix, quickly open autoclave, take out foamed thermoplasticity
Polyurethane elastomer expanded bead.
The internal structure of expanded bead manufactured in the present embodiment is as shown in Figure 1.
Embodiment 2：The present embodiment and the difference of embodiment 1 are thermoplastic polyurethane elastomer bead in 10MPa nitrogen
Normal temperature dipping 15 hours in atmosphere, 100 DEG C of blowing temperature, foam dwell pressure 7MPa, foams 12 minutes dwell times.
Embodiment 3：The present embodiment and the difference of embodiment 1 are thermoplastic polyurethane elastomer bead in 20MPa nitrogen
Normal temperature dipping 5 hours in atmosphere, 180 DEG C of blowing temperature, foam dwell pressure 8MPa, foams 7 minutes dwell times.
Embodiment 4：It is 200,000 by 100g mean molecule quantities, average diameter is 2mm block polyetheramides elastomer (block
Polyetheramide elastomeric body) bead, put into the autoclave under normal temperature and seal autoclave, open intake valve, be passed through nitrogen, make
Bead normal temperature saturation in 30MPa nitrogen atmosphere impregnates 8 hours.
Thereafter the nitrogen pressure in slow discharge kettle, opens autoclave, takes out the bead for having absorbed nitrogen, put it into
In another autoclave for reaching 220 DEG C of blowing temperature of setting, autoclave is sealed, 20MPa carbon dioxide, pressurize is passed through
6 minutes, air bleeding valve is quickly opened, the carbon dioxide of autoclave is excluded, causes the nucleation of abscess and growth in matrix, quickly
Autoclave is opened, foamed bead is taken out.
The internal structure of expanded bead manufactured in the present embodiment is as shown in Figure 2.
Embodiment 5：The present embodiment and the difference of embodiment 4 are block polyetheramides elastomer bead in 20MPa nitrogen
Normal temperature dipping 10 hours in atmosphere, 250 DEG C of blowing temperature, foam dwell pressure 25MPa, foams 5 minutes dwell times.
Embodiment 6：The present embodiment and the difference of embodiment 4 are block polyetheramides elastomer bead in 40MPa nitrogen
Normal temperature dipping 5 hours in atmosphere, 350 DEG C of blowing temperature, foam dwell pressure 15MPa, foams 9 minutes dwell times.
Embodiment 7：It is 160,000 by 100g mean molecule quantities, average diameter is 4mm polyolefin elastomer (POE) bead,
In autoclave under input normal temperature and autoclave is sealed, open intake valve, be passed through nitrogen, polyolefin elastomer bead is existed
Normal temperature saturation impregnates 20 hours in 10MPa nitrogen atmosphere.
Thereafter the nitrogen pressure in slow discharge kettle, opens autoclave, takes out the polyolefin elastomer pearl for having absorbed nitrogen
Grain, puts it into another autoclave for having reached 110 DEG C of blowing temperature of setting, autoclave is sealed, is passed through 15MPa's
Air bleeding valve is quickly opened in carbon dioxide, pressurize 15 minutes, is excluded the carbon dioxide of autoclave, is caused polyolefin elastomer
The nucleation of abscess and growth in matrix, quickly open autoclave, take out foamed polyolefin elastomer bead.
The internal structure of expanded bead manufactured in the present embodiment is as shown in Figure 3.
Embodiment 8：The difference of the present embodiment and embodiment 7 is polyolefin elastomer bead in 5MPa nitrogen atmospheres often
Temperature dipping 20 hours, 60 DEG C of blowing temperature, foam dwell pressure 30MPa, foams 12 minutes dwell times.
Embodiment 9：The present embodiment and the difference of embodiment 7 are polyolefin elastomer bead in 17MPa nitrogen atmospheres
Normal temperature dipping 14 hours, 80 DEG C of blowing temperature, foam dwell pressure 25MPa, foams 20 minutes dwell times.
Embodiment 10：It is 120,000 by 100g mean molecule quantities, average diameter is 3mm thermoplastic polyester elastomer (TPEE)
In autoclave under bead, input normal temperature and autoclave is sealed, open intake valve, be passed through nitrogen, make thermoplastic polyester elastomer
Body bead saturation 2 hours in 50MPa nitrogen atmosphere.
Thereafter the nitrogen pressure in slow discharge kettle, opens autoclave, takes out the thermoplastic polyester elastomer for having absorbed nitrogen
Body bead, puts it into another autoclave for having reached 160 DEG C of blowing temperature of setting, autoclave is sealed, is passed through
Air bleeding valve is quickly opened in 14MPa carbon dioxide, pressurize 6 minutes, is excluded the carbon dioxide of autoclave, is caused thermoplasticity
The nucleation of abscess and growth in polyester elastomer matrix, quickly open autoclave, take out foamed thermoplastic polyester elastomer
Body bead.
The internal structure of expanded bead manufactured in the present embodiment is as shown in Figure 4.
Embodiment 11：The present embodiment and the difference of embodiment 10 are thermoplastic polyester elastomer bead in 40MPa nitrogen
Normal temperature dipping 6 hours in atmosphere, 230 DEG C of blowing temperature, foam dwell pressure 10MPa, foams 5 minutes dwell times.
Embodiment 12：The present embodiment and the difference of embodiment 10 are thermoplastic polyester elastomer bead in 60MPa nitrogen
Normal temperature dipping 2 hours in atmosphere, 110 DEG C of blowing temperature, foam dwell pressure 12MPa, foams 8 minutes dwell times.
Thermoplastic elastomer foaming bead in above-described embodiment is tested, method of testing is as follows：Using plum Teller-
XSE assay balance of the benefit with density component is held in the palm, the density of expanded bead is measured, the volumetric expansion times for obtaining expanded bead is calculated
Rate, volume expansion ratio (Rex)=ρpolymer/ρfoam, wherein, ρpolymerFor the density of former bead, ρfoamFor the close of expanded bead
Degree.Expanded bead is quenched disconnected through liquid nitrogen cooling, section metal spraying observes the abscess inside expanded bead using SEM
Structure, test result is as shown in the table.
It can be seen that the method for preparing thermoplastic elastomer foaming bead provided by the present invention from above-described embodiment
The expanded bead product of preparation has higher expansion ratio.
Reason is that the present invention is improved existing supercritical carbon dioxide foaming technology, high by normal temperature first
Nitrogen dipping is pressed, nitrogen molecule is dissolved in inside thermoplastic elastomer (TPE) bead before foaming, then again in HTHP
Carbon dioxide molecule is dissolved in inside thermoplastic elastomer (TPE) bead under super critical condition, by unexpected pressure release, induce abscess
Nucleation and growth, prepare thermoplastic elastomer foaming bead.Described thermoplastic elastomer foaming bead gas when foaming completion
It is nitrogen and carbon dioxide gas mixture that bubble is internal.
Described thermoplastic elastomer foaming bead is positioned in air after the completion of foaming, and bubble is inside and outside to occur gas friendship
Change, the carbon dioxide in bubble is outwards escaped rapidly.But nitrogen escape rate is low inside bubble and pressure is higher than outside air,
It can keep having enough air pressure inside bubble in gas exchange process, to play a part of supporting bubble structure.Can be effective
The low caused bubble volume contraction process of the bubble internal pressure present in pure carbon dioxide foam process is avoided, so as to tie up
Hold the higher expansion ratio of thermoplastic elastomer foaming bead.
The key of above-mentioned technical proposal is to be to realize inside thermoplastic elastomer foaming bead to be nitrogen and carbon dioxide
Mixed gas.Its difficult point is that the diffusion rate and solubility of nitrogen are all relatively low, to be sent out using nitrogen and carbon dioxide mix
Bubble gas is foamed, it is necessary to configure high pressure environment, and longer is swelled diffusion time.Titanium dioxide Carbon diffusion is fast simultaneously
It is much higher that rate compares nitrogen with solubility, therefore enter inside expanded bead and be mainly carbon dioxide and nitrogen content is few,
Deficiency plays a part of maintaining bubble volume.
And the method that the technical program is impregnated using nitrogen normal temperature high voltage solves this technical barrier, normal temperature dipping can be with
Nitrogen solubility is effectively improved, nitrogen adsorption amount is improved, and reduces energy consumption and technical difficulty, thermoplastic elastomer (TPE) is absorbed foot
Enough nitrogen is to maintain bubble structure.Impregnation pressure is 5-60MPa, small compared to the simple pressure requirements using nitrogen gas foaming
Pressure requirements that are many, being foamed again smaller than carbon dioxide nitrogen mixed gas, therefore high pressure resistant equipment configratioin requirement is low, enters one
Step reduces technical difficulty.
Impregnate after nitrogen, then foamed using supercritical carbon dioxide, it is possibility to have effect is avoided in expanded bead bubble
The few situation of nitrogen based on portion's carbon dioxide.Make to have enough nitrogen inside expanded bead for supporting bubble structure,
While solving inside and outside bubble in gas exchange process that air pressure in bubble is low to cause the bubble volume to reduce problem, higher hair is maintained
Multiplying power is steeped, producting process difficulty is reduced, production efficiency is improved, it is easier to Technique Popularizing and industrialization.
Claims (10)
1. a kind of method for preparing thermoplastic elastomer foaming bead, it is characterized in that, methods described includes,
1) nitrogen impregnation steps,
Thermoplastic elastomer (TPE) particle impregnates in high pressure nitrogen atmosphere, and dipping temperature is normal temperature, obtains the heat for fully absorbing nitrogen
Thermoplastic elastic particle；
2) carbonic maceration step,
The thermoplastic elastomer (TPE) particle for fully absorbing nitrogen is placed in supercritical carbon dioxide, progress is swelled diffusion,
Obtain the thermoplastic elastomer (TPE) particle of dissolving nitrogen and carbon dioxide；
3) expansion step,
The thermoplastic elastomer (TPE) particle foaming and intumescing of induction dissolving nitrogen and carbon dioxide, is made thermoplastic elastomer foaming pearl
It is nitrogen and carbon dioxide gas mixture inside grain, the thermoplastic elastomer foaming bead.
2. the method according to claim 1 for preparing thermoplastic elastomer foaming bead, it is characterized in that, the nitrogen dipping
Step further comprises：Thermoplastic elastomer (TPE) particle impregnates in 5-60MPa high pressure nitrogens, and dipping temperature is normal temperature, during dipping
Between be 2-20 hour, nitrogen molecule is diffused into thermoplastic elastomer (TPE) particle, and acquisition fully absorbs the thermoplastic elastic of nitrogen
Body particle.
3. the method according to claim 1 for preparing thermoplastic elastomer foaming bead, it is characterized in that, the carbon dioxide
Impregnation steps further comprise, the thermoplastic elastomer (TPE) particle for fully absorbing nitrogen is placed in the closed vessel of blowing temperature,
The supercritical carbon dioxide for meeting blow pressure is passed through, diffusion 5-20 minutes is swelled, dissolving nitrogen and carbon dioxide is obtained
Thermoplastic elastomer (TPE) particle.
4. the method according to claim 3 for preparing thermoplastic elastomer foaming bead, it is characterized in that, the blowing temperature
Can occur plastic deformation, but the temperature that can't be flowed for thermoplastic elastomer (TPE) particle, for amorphous polymer, blowing temperature
Within Tg~Tg+40 DEG C, Tg is the glass transition temperature of amorphous polymer；For crystalline polymer, blowing temperature exists
Within Tm-20 DEG C~Tm, Tm is the fusing point of crystalline polymer.
5. the method according to claim 3 for preparing thermoplastic elastomer foaming bead, it is characterized in that, blowing temperature is
60 °~350 °.
6. the method according to claim 3 for preparing thermoplastic elastomer foaming bead, it is characterized in that, supercriticality two
Carbon oxide pressure is 7~30MPa.
7. the method according to claim 1 for preparing thermoplastic elastomer foaming bead, it is characterized in that, the expansion step
Further comprise, quick pressure releasing induction it is described dissolving nitrogen and carbon dioxide thermoplastic elastomer (TPE) particle in abscess nucleation and
Growth, it is that nitrogen and carbon dioxide are mixed to be made inside thermoplastic elastomer foaming bead, the thermoplastic elastomer foaming bead
Close gas.
8. the method for preparing thermoplastic elastomer foaming bead according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7, its
It is characterized in that thermoplastic elastomer (TPE) particle is TPUE particle, block polyetheramides elastomer particle, polyolefin
Elastomer particle, thermoplastic polyester elastomer particle one of which or several combinations.
9. the method according to claim 8 for preparing thermoplastic elastomer foaming bead, it is characterized in that, thermoplastic elastomer (TPE)
The number-average molecular weight of particle is 1~6,000,000.
10. the method according to claim 8 for preparing thermoplastic elastomer foaming bead, it is characterized in that, thermoplastic elastic
The particle diameter 0.5-10mm of body particle.
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| CN107746570A (en) * | 2017-09-26 | 2018-03-02 | 上海德亿化工有限公司 | A kind of polyamide expanded material its preparation method |
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| CN109836801A (en) * | 2019-02-15 | 2019-06-04 | 美瑞新材料股份有限公司 | A kind of silica gel and thermoplastic elastomer foaming bead composite material and preparation method and application |
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| CN111718514A (en) * | 2020-05-14 | 2020-09-29 | 福建兴迅新材料科技有限公司 | Preparation process of ultralight thermoplastic elastomer foam material |
| CN113201166A (en) * | 2021-05-31 | 2021-08-03 | 江苏中科聚合新材料产业技术研究院有限公司 | High-magnification high-rigidity foaming amorphous polyester bead and preparation method thereof |
| CN114350008A (en) * | 2022-01-07 | 2022-04-15 | 中化学科学技术研究有限公司 | Nylon foamed sheet with high foaming ratio and preparation method thereof |
| CN116144065A (en) * | 2023-01-10 | 2023-05-23 | 安踏（中国）有限公司 | Preparation method of high-elasticity cushioning foaming material and sole |
| CN116655990A (en) * | 2023-05-30 | 2023-08-29 | 苏州申赛新材料有限公司 | Foaming method of thermoplastic elastomer and application thereof |
| CN110305359B (en) * | 2019-07-31 | 2024-06-11 | 苏州申赛新材料有限公司 | Device for preparing foaming particles by using supercritical fluid |
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| KR102263684B1 (en) | 2017-10-31 | 2021-06-10 | 창저우 시앙 뉴 머티리얼즈 테크놀로지 컴퍼니 리미티드 | Method for producing block polyether amide expanded particles having a sandbag structure |
| WO2019085158A1 (en) * | 2017-10-31 | 2019-05-09 | 常州市顺祥新材料科技股份有限公司 | Method for preparing block polyether amide foamed particle with sandbag structure |
| JP2019535876A (en) * | 2017-10-31 | 2019-12-12 | チャンヂョウ シュンシァン ニュー マテリアルズ テクノロジー カンパニー リミテッドＣｈａｎｇｚｈｏｕ Ｓｈｕｎｘｉａｎｇ Ｎｅｗ Ｍａｔｅｒｉａｌｓ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ | Process for producing block polyetheramide foam granules containing a sandbag structure |
| KR20190104058A (en) * | 2017-10-31 | 2019-09-05 | 창저우 ?시앙 뉴 머티리얼즈 테크놀로지 컴퍼니 리미티드 | Process for producing block polyether amide foam particles having a sandbag structure |
| CN107629448A (en) * | 2017-10-31 | 2018-01-26 | 常州市顺祥新材料科技有限公司 | A kind of preparation method with sandbag structure block polyetheramides expanded particle |
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| CN110305359B (en) * | 2019-07-31 | 2024-06-11 | 苏州申赛新材料有限公司 | Device for preparing foaming particles by using supercritical fluid |
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| CN110524781A (en) * | 2019-09-02 | 2019-12-03 | 厦门市锋特新材料科技有限公司 | A kind of TPU sheet foaming process |
| WO2021227613A1 (en) * | 2020-05-14 | 2021-11-18 | 福建兴迅新材料科技有限公司 | Method for preparing ultra-light thermoplastic elastomer foaming material |
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| CN113201166A (en) * | 2021-05-31 | 2021-08-03 | 江苏中科聚合新材料产业技术研究院有限公司 | High-magnification high-rigidity foaming amorphous polyester bead and preparation method thereof |
| CN114350008A (en) * | 2022-01-07 | 2022-04-15 | 中化学科学技术研究有限公司 | Nylon foamed sheet with high foaming ratio and preparation method thereof |
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Application publication date: 20170919 |