CN110183713A - A kind of preparation method of polybutene expanded bead (EPB) - Google Patents

A kind of preparation method of polybutene expanded bead (EPB) Download PDF

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Publication number
CN110183713A
CN110183713A CN201910557601.5A CN201910557601A CN110183713A CN 110183713 A CN110183713 A CN 110183713A CN 201910557601 A CN201910557601 A CN 201910557601A CN 110183713 A CN110183713 A CN 110183713A
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polybutene
agent
expanded bead
epb
preparation
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CN110183713B (en
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宫瑞英
韩冲
李朝旭
孙并臻
康力强
迟守波
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Qingdao Qingmai High Energy Electron Irradiation Co ltd
Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Qingmai High Energy Electron Irradiation Co ltd
Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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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
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • 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
    • 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
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of preparation method of polybutene expanded bead, and the expanded bead uses polybutene alloy powder to be foamed and be made by intermittent autoclave foaming using physical blowing agent for basic resin.Wherein the polybutene alloy introduces other polyolefin components, effectively improves crystal transfer speed, shock resistance of polybutene etc. by alloy technology synthesis in kettle.The polybutene alloy of the present invention using high molecular weight, wide molecular weight distribution is used as raw material, and (190 DEG C, 2.16kg) of melt flow index are 0.1-2g/10min.Polybutene alloy melt intensity is high, and blowing temperature section is wide, and different auxiliary agents is used in combination, and can prepare uniform foam cell densification, the adjustable closed-cell foam bead of cell diameter.Polybutene alloy expanded bead (EPB) prepared by the present invention is a kind of resistance to compression buffering heat-barrier material, with excellent high-intensitive anti-retraction, damping energy absorption capacity, lower temperature resistance, chemical corrosion resistance, it is readily molded into type, have that at low cost, the period is short simultaneously, and density it is controllable the advantages that, can be widely used for the fields such as military project, automobile, building, toy for children, packaging material for food, household electrical appliance.

Description

A kind of preparation method of polybutene expanded bead (EPB)
Technical field
The present invention relates to high molecular foam material technical fields, more particularly, it relates to which a kind of polybutene foams Bead (EPB) and preparation method thereof.
Technical background
Foamed plastics is the aggregation formed and gas is dispersed in solid polymer, and foamed material has weight Gently, the advantages that heat-insulated, buffering insulate, corrosion resistant, cheap.Therefore, it is widely used in daily necessities, packaging, industry, agricultural, fortune It is defeated, war industry and aerospace industry.Compared with conventional foam, non-crosslinked polyolefin foam has excellent machine Tool performance and environmental-protecting performance.Wherein the polybutene in polyolefin has good lower temperature resistance, and creep resistance, corrosion resistance is good Good mechanical property and mechanical strength, compared with other polyolefin, anti-stress cracking performance is best.Polybutene alloy is logical It crosses alloy technology in kettle to synthesize, introduces other polyolefin components, effectively improve crystal transfer speed, the shock resistance of polybutene Deng.Polybutene alloy has the characteristics that high molecular weight, wide molecular weight distribution, therefore polybutene alloy melt intensity is high, foaming temperature It is wide to spend section, different machining function auxiliary agents is used in combination, uniform foam cell densification can be prepared, cell diameter is adjustable to be closed Hole expanded bead.
Intermittent autoclave foaming generally uses physical blowing agent, raw using the pressure drop difference in reaction kettle between atmospheric pressure Produce the expanded bead containing hole-closing structure.Common physical blowing agent has volatile hydrocarbon, CO2、N2Deng reaction process In will not chemically react, greatly reduce the risk of reaction, and will not environment pollute, it is low in cost.
Currently, the utilization rate of China's polybutene is lower, it is mainly used in the pipelines such as running water pipe, hot-water line and steam heating pipe Pipe wall material.Polybutene expanded bead (EPB) has high intensity, high tenacity, has good low temperature resistant, damping resilience, together When production process in without any pollutant, no volatile organic substance has no irritating odor, and can satisfy automobile interior decoration, food The strict demand of packed and transported, household electrical appliance, interior decoration to smell.Simultaneously EPB excellent lower temperature resistance can guarantee its Still has excellent intensity and toughness in ultra-low temperature surroundings.Therefore polybutene foamed material (EPB) has vast potential for future development.
In order to preferably utilize resource, expands the application field of polybutene, improve the utilization rate of polybutene, promote China's hair The development of industry is steeped, the present invention proposes a kind of polybutene foaming material excellent as foamed substrate processability using polybutene alloy The method of material.
Summary of the invention
Not high for current polybutene stock utilization, the problems such as application field is small, the present invention provides a kind of polybutene and closes Golden hair foam material and preparation method thereof provides a kind of simple production process under the premise of keeping mechanical property, environmentally friendly High-performance polybutene foamed material.
A kind of 1 preparation method of polybutene expanded bead (EPB) of the present invention, specific formula are as follows: with weight hundred Score meter, is made of following raw material: polybutene alloy powder is as basic resin, dosage 80%~95%；Nucleating agent 3%~ 7%, antioxidant 0.1%~0.5%, processing aid 2%~15%.
2 polybutene alloy powders of the present invention are that (molar content is 50%- to butylene to 1- butylene in the copolymer 99%) with propylene (molar content is 0%-15% to propylene in the copolymer), (molar content is ethylene ethylene in the copolymer 0%-15%), (molar content is 0%-20%) to 1- amylene to 1- amylene in the copolymer, (1- hexene is altogether for 1- hexene Molar content is 0%-20% in polymers), 1- heptene (molar content is 0%-20% to 1- heptene in the copolymer), 1- Octene (1- octene in the copolymer molar content be 0%-20%), 1- nonene (1- nonene molar content in the copolymer To be any in 0%-20%), 1- decene (molar content is 0%-20% to 1- decene in the copolymer) comonomer or Two or more copolymers, molecular weight of copolymer are distributed Mw/Mn=2-20, melt flow index (190 DEG C, 2.16Kg) 0.1- 2g/10min。
3 preparation methods of the present invention are intermittent autoclave foaming.
4 physical blowing agents of the present invention include volatile hydrocarbon, CO2、N2In any one, wherein excellent Select CO2。
5 nucleating agents of the present invention are the compound of β crystallization nucleating agent and α crystallization nucleating agent.Wherein β crystallization nucleation Agent is that organic carboxyl acid and its esters (refer to the salt of dicarboxylic acids and the IIth A race metallic element, especially pimelic acid and stearic acid The binary complex of calcium), one of aromatic amides class TMB series and rare earth compounding WBG series or including two kinds and two kinds Above mixture.α crystallization nucleating agent is organic carboxyl acid and its esters, aromatic amides class, with the inorganic of α crystallization nucleation function One or more of series such as nucleating agent, α crystallization nucleating agent aromatic carboxylic acids salt, α crystallization nucleating agent glucitols, it is total to be nucleated Agent dosage is 0.001~3 part.It is preferred that β crystallization nucleating agent is aromatic amides class TMB series or rare earth compounding WBG series, α knot Brilliant nucleating agent is the inorganic nucleator of α crystallization nucleation function, and the further preferred total dosage of nucleating agent is 0.01~2 part.
6 processing aids of the present invention are one of antioxidant, antistatic agent, fire retardant, Masterbatch, coupling agent Or it is several.Auxiliary dosage is 2~15 parts, preferably 5-12 parts.
7 foaming nucleation agent of the present invention be talcum powder, mica, bead, silica, calcium carbonate, montmorillonite, One or more of kaolin, aluminium oxide, barium sulfate, zinc oxide, zinc stearate, calcium stearate；The antioxidant is antioxygen One or more of agent 168,1010,1076,626；The antistatic agent is alkyl imidazoline class, quaternary phosphonium salt, season sulfosalt One or more of class, quaternary ammonium salt, alkyl sulfonates or phosphoric acid salt；The fire retardant is magnesium hydroxide, hydroxide One or more of aluminium, zinc borate, expansion type flame retardant DTPB；The coupling agent be silane coupling agent, titanate coupling agent, One or more of aluminate coupling agent.
1) in above-mentioned foaming nucleation agent, preferably one of nanometer calcium carbonate, talcum powder, silica, montmorillonite or It is several；
2) in above-mentioned antioxidant, preferably 1010, one or both of 168；
3) in above-mentioned antistatic agent, preferably one or more of quaternary phosphonium salt, season sulfosalt class, quaternary ammonium salt；
4) in above-mentioned fire retardant, preferably one or more of magnesium hydroxide, aluminium hydroxide, zinc borate；
5) in above-mentioned coupling agent, preferably silane coupling agent.
A kind of 8 preparation methods of polybutene expanded bead (EPB) of the present invention, foaming method is according to the following steps It carries out:
1) polybutene alloy powder used, nucleating agent will be tested, processing aid is placed in 40 DEG C~60 DEG C of vacuum oven Middle 18~48h of drying；
2) raw material after proportionally weighing drying, wherein by weight percentage, being made of following raw material: polybutene closes Bronze material is as basic resin, dosage 80%~95%；Nucleating agent 3%~7%, antioxidant 0.1%~0.5%, preferably 0.2%~0.3%, processing aid 2%~15%, preferably 5%~12%.Raw material after weighing is placed in automatic mixing machine In, stir 2~5min；
3) mixing is added twin-screw extrude, there are six temperature range, temperature settings for the double screw extruder It is 120 DEG C~160 DEG C；After supercooling, pelletizing, drying, long 1-2mm, the modification polybutene particle of diameter 0.5-2mm are obtained；
4) by polybutene particle, dispersing agent, deionized water is put into autoclave, under agitation by physical blowing agent It is injected into autoclave, while the temperature of autoclave is increased to 110-130 DEG C, pressure rise to 2.0-10.0MPa reaches and sets After fixed temperature and pressure, 20-60min is kept, penetrates into foaming agent in polybutene particle；
5) above-mentioned dispersing agent be kaolin, stearic acid, neopelex, quaternary ammonium compound, lecithin, amino acid, Glycine betaine, fatty glyceride, one or more of fatty acid sorbitan (sorbitan fatty acid ester).Preferably yin from Subtype surfactant sodium dodecyl base benzene sulfonic acid sodium salt, dispersing agent kaolin.
6) after dwell time, by autoclave with certain pressure release speed discharge, it is cooling that polybutene bead spurts into cold water System obtains polybutene expanded bead of the expansion ratio between 2-30 times；By the polybutene expanded bead tentatively obtained two In secondary foam device, in vapor atmosphere, pressure 0.1-1.5MPa is controlled, discharge after 10~60s is kept, further obtains more High expansion ratio polybutene expanded bead, expansion ratio is at 15-60 times.
7) polybutene expanded bead dry 10~48h in 30~60 DEG C of environment is prepared, the polybutene after drying is foamed Bead is injected into vapor compression molding device, by vapor heating, cooling, obtains polybutene expanded bead formed body.
The depressurization rate of 9 autoclaves of the present invention is 0.3-2.0MPa/s, preferably 1.0-2.0MPa/s.Polybutene Bead-aqueous dispersion mixture cooling rate is 10-25 DEG C/s.
10 compared with prior art, the present invention have following preferential:
Polybutene foamed material of the invention has high intensity, high tenacity, has good low temperature resistant, damping resilience, With good mechanical property, and distribution of cells is uniform.Using physical blowing agent as foaming agent, uncontaminated gases in production process Discharge.And polybutene expanded bead prepared by the present invention can realize that abscess is adjusted, abscess-size greatly expands close to micron order The application of polybutene material.105670137 A of CN utilizes chemical foaming agent, prepares polybutene foaming by moulded from foam method Material, cell size are not easily controlled and be easy to cause environmental pollution.And China's polybutene is mainly used in hot-water line at present Equal tubular materials, polybutene material application field is smaller at present, and the polybutene expanded bead preparation method that the present invention develops expands Wide polybutene application field, promotes the development of China's polybutene industry, has preferable realistic meaning.
Specific implementation method
Embodiment 1
1) experiment polybutene powder 300g, inorganic nucleator talcum powder 1g are placed in 50 DEG C of vacuum oven, are done It is dry for 24 hours；
2) by auxiliary agent according to formula rate by weight percentage, mixed with resin raw material and nucleating agent with automatic mixing machine Uniformly, premix is obtained.Premix is added twin-screw extrude through barrel, screw speed 80r/min, from spout It is followed successively by one to six area to head, temperature is respectively set to 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, 140 DEG C.Through double spiral shells Bar squeezes out water cooling bracing pelletizing, obtains long 1.5mm, the modification polybutene small particles of diameter 1.2mm；
3) polybutene particle, dispersing agent (kaolin), surfactant (neopelex), deionized water are thrown Enter into autoclave, relative to 100 parts by weight of polybutene particles, 1 part of kaolin is added, 0.75 part of surfactant, 200 parts are gone Ionized water.Physical blowing agent is injected into autoclave under agitation, stirring rate 700r/min；Simultaneously by autoclave Temperature be increased to 125 DEG C, pressure rise to 7.5MPa after the temperature and pressure for reaching setting, keeps 30min, makes foaming agent It penetrates into polybutene particle；
4) by the controllable discharge speed 1.0MPa/s of autoclave, polybutene particle-high pressure water dispersion mixing material is spurted into cold Water cooling system in vapor atmosphere, controls pressure by the polybutene expanded bead tentatively obtained in second time of foaming device 0.3MPa keeps 30s, and discharge further obtains higher expansion ratio polybutene expanded bead, and expansion ratio is at 22~30 times Between, cell density is 0.03~0.04g/cm3Between.
5) polybutene expanded bead dry 12h in 60 DEG C of environment is prepared, the polybutene expanded bead after drying is injected Polybutene expanded bead formed body is obtained by vapor heating, cooling to vapor compression molding device.
Embodiment 2
1) experiment polybutene powder 300g, inorganic nucleator montmorillonite 1g are placed in 50 DEG C of vacuum oven, are done It is dry for 24 hours；
2) by auxiliary agent according to formula rate by weight percentage, mixed with resin raw material and nucleating agent with automatic mixing machine Uniformly, premix is obtained.Premix is added twin-screw extrude through barrel, screw speed 80r/min, from spout It is followed successively by one to six area to head, temperature is respectively set to 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, 140 DEG C.Through double spiral shells Bar squeezes out water cooling bracing pelletizing, obtains long 1.5mm, the modification polybutene small particles of diameter 1.2mm；
3) polybutene particle, dispersing agent (kaolin), surfactant (neopelex), deionized water are thrown Enter into autoclave, relative to 100 parts by weight of polybutene particles, 1 part of kaolin is added, 0.75 part of surfactant, 200 parts are gone Ionized water.Physical blowing agent is injected into autoclave under agitation, stirring rate 700r/min；Simultaneously by autoclave Temperature be increased to 125 DEG C, pressure rise to 7.5MPa after the temperature and pressure for reaching setting, keeps 20min, makes foaming agent It penetrates into polybutene particle；
4) by the controllable discharge speed 2.0MPa/s of autoclave, polybutene particle-high pressure water dispersion mixing material is spurted into cold Water cooling system in vapor atmosphere, controls pressure by the polybutene expanded bead tentatively obtained in second time of foaming device 0.3MPa keeps 30s, and discharge further obtains higher expansion ratio polybutene expanded bead, and expansion ratio is at 25~30 times Between, cell density is 0.03~0.035g/cm3Between.
5) polybutene expanded bead dry 12h in 60 DEG C of environment is prepared, the polybutene expanded bead after drying is injected Polybutene expanded bead formed body is obtained by vapor heating, cooling to vapor compression molding device.
Embodiment 3
1) experiment polybutene powder 300g, inorganic nucleator silica 2g are placed in 50 DEG C of vacuum oven, Drying is for 24 hours；
2) by auxiliary agent according to formula rate by weight percentage, mixed with resin raw material and nucleating agent with automatic mixing machine Uniformly, premix is obtained.Premix is added twin-screw extrude through barrel, screw speed 100r/min, from spout It is followed successively by one to six area to head, temperature is respectively set to 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, 140 DEG C.Through double spiral shells Bar squeezes out water cooling bracing pelletizing, obtains long 1.5mm, the modification polybutene small particles of diameter 1.2mm；
3) polybutene particle, dispersing agent (kaolin), surfactant (neopelex), deionized water are thrown Enter into autoclave, relative to 100 parts by weight of polybutene particles, is added 1.2 parts of kaolin, 0.75 part of surfactant, 200 parts Deionized water.Physical blowing agent is injected into autoclave under agitation, stirring rate 700r/min；Simultaneously by high pressure The temperature of kettle is increased to 128 DEG C, pressure rise to 7.5MPa, after the temperature and pressure for reaching setting, keeps 20min, makes to foam Agent penetrates into polybutene particle；
4) by the controllable discharge speed 1.0MPa/s of autoclave, polybutene particle-high pressure water dispersion mixing material is spurted into cold Water cooling system in vapor atmosphere, controls pressure by the polybutene expanded bead tentatively obtained in second time of foaming device 0.3MPa keeps 30s, and discharge further obtains higher expansion ratio polybutene expanded bead, and expansion ratio is at 14~15 times Between, cell density is 0.06~0.065g/cm3Between.
5) polybutene expanded bead dry 12h in 60 DEG C of environment is prepared, the polybutene expanded bead after drying is injected Polybutene expanded bead formed body is obtained by vapor heating, cooling to vapor compression molding device.
Embodiment 4
1) experiment polybutene powder 300g, inorganic nucleator nanometer calcium carbonate 1g are placed in 50 DEG C of vacuum oven In, drying is for 24 hours；
2) by auxiliary agent according to formula rate by weight percentage, mixed with experimental raw and nucleating agent with automatic mixing machine Uniformly, premix is obtained.Premix is added twin-screw extrude through barrel, screw speed 80r/min, from spout It is followed successively by one to six area to head, temperature is respectively set to 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 150 DEG C, 140 DEG C.Through double spiral shells Bar squeezes out water cooling bracing pelletizing, obtains long 1.5mm, the modification polybutene small particles of diameter 1.0mm；
3) polybutene particle, dispersing agent (kaolin), surfactant (neopelex), deionized water are thrown Enter into autoclave, relative to 100 parts by weight of polybutene particles, 1 part of kaolin is added, 0.75 part of surfactant, 200 parts are gone Ionized water.Physical blowing agent is injected into autoclave under agitation, stirring rate 700r/min；Simultaneously by autoclave Temperature be increased to 125 DEG C, pressure rise to 10MPa after the temperature and pressure for reaching setting, keeps 30min, seeps foaming agent Thoroughly into polybutene particle；
4) by the controllable discharge speed 2.0MPa/s of autoclave, polybutene particle-high pressure water dispersion mixing material is spurted into cold Water cooling system in vapor atmosphere, controls pressure by the polybutene expanded bead tentatively obtained in second time of foaming device 0.5MPa keeps 30s, and discharge further obtains higher expansion ratio polybutene expanded bead, and expansion ratio is at 30~45 times Between, cell density is 0.02~0.025g/cm3Between.
5) polybutene expanded bead dry 12h in 60 DEG C of environment is prepared, the polybutene expanded bead after drying is injected Polybutene expanded bead formed body is obtained by vapor heating, cooling to vapor compression molding device.
Above-described embodiment elaborates the present invention.Certainly, above description is not limitation of the present invention, the present invention Be also not limited to above-mentioned example, related technical personnel within the essential scope of the present invention made variation, retrofit, add and add deduct Less, it replaces, also belongs to protection scope of the present invention.

Claims (11)

1. a kind of preparation method of polybutene expanded bead (EPB), it is characterised in that: by weight percentage, by following raw material Composition: polybutene alloy powder is as basic resin, dosage 80%~95%；Nucleating agent 3%~7%, antioxidant 0.1%~ 0.5%, processing aid 2%~15%.
2. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that described Polybutene alloy powder is that (propylene is in copolymer with propylene for 1- butylene (molar content is 50%-99% to butylene in the copolymer) Middle molar content is 0%-15%), ethylene (molar content is 0%-15% to ethylene in the copolymer), 1- amylene (1- penta Molar content is 0%-20% to alkene in the copolymer), (molar content is 0%- to 1- hexene to 1- hexene in the copolymer 20%), 1- heptene (1- heptene in the copolymer molar content be 0%-20%), (1- octene is in the copolymer for 1- octene Molar content is 0%-20%), 1- nonene (1- nonene in the copolymer molar content be 0%-20%), 1- decene Any one or more copolymers, copolymerization in (molar content is 0%-20% to 1- decene in the copolymer) comonomer Object molecular weight distribution mw/mn=2-20, melt flow index (190 DEG C, 2.16Kg) 0.1-2g/10min.
3. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that described Preparation method is intermittent autoclave foaming.
4. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that described Physical blowing agent includes volatile hydrocarbon, CO2、N2In any one or combinations thereof object.
5. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that described Nucleating agent is the compound of β crystallization nucleating agent and α crystallization nucleating agent.Wherein β crystallization nucleating agent is that organic carboxyl acid and its esters (refer to Be dicarboxylic acids and the IIth A race metallic element salt, the especially binary complex of pimelic acid and calcium stearate), fragrant acyl One or both of amine TMB series and rare earth compounding WBG series and two or more mixtures；α crystallization nucleating agent is Organic carboxyl acid and its esters, aromatic amides class, the inorganic nucleator with α crystallization nucleation function, α crystallization nucleating agent aromatic carboxylic acids One or more of series such as salt, α crystallization nucleating agent glucitols.Total nucleating agent dosage is 0.001~3 part.
6. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that described Processing aid is one or more of foaming nucleation agent, antioxidant, antistatic agent, fire retardant, Masterbatch, coupling agent.Auxiliary agent Dosage is 2~15 parts.
7. a kind of preparation method of polybutene expanded bead (EPB) according to claim 1, which is characterized in that right is wanted Ask foaming nucleation agent in 6 auxiliary agents be talcum powder, mica, bead, silica, calcium carbonate, montmorillonite, kaolin, One or more of aluminium oxide, barium sulfate, zinc oxide, zinc stearate, calcium stearate；The antioxidant be irgasfos 168, 1010, one or more of 1076,626；The antistatic agent is alkyl imidazoline class, quaternary phosphonium salt, season sulfosalt class, quaternary ammonium Salt, alkyl sulfonates or phosphoric acid salt；The fire retardant is magnesium hydroxide, aluminium hydroxide, zinc borate, expansion type flame retardant One or more of DTPB；The coupling agent be one of silane coupling agent, titanate coupling agent, aluminate coupling agent or It is several.
8. a kind of preparation method of polybutene expanded bead (EPB) described according to claim 1~any one of 7, special Sign is that foaming method follows the steps below:
1) polybutene alloy powder used, nucleating agent will be tested, processing aid is placed in 40 DEG C~60 DEG C of vacuum oven and does Dry 18~48h；
2) each raw material after proportionally weighing drying, wherein by weight percentage, being made of following raw material: polybutene alloy Powder is as basic resin, dosage 80%~95%；Nucleating agent 3%~7%, antioxidant 0.1%~0.5%, processing aid 2% ~15%.Raw material after weighing is placed in automatic mixing machine, 2~5min is stirred；
3) mixing is added twin-screw extrude, after supercooling, pelletizing, drying, obtains long 1-2mm, diameter 0.5-2mm's Modified polybutene particle；
4) it will be modified polybutene particle, dispersing agent, deionized water is put into autoclave, under agitation by physical blowing agent It is injected into autoclave, while the temperature of autoclave is increased to 110-130 DEG C, pressure rise to 2.0-6.0MPa reaches and sets After fixed temperature and pressure, 20-60min is kept, penetrates into foaming agent in polybutene particle；
5) after dwell time, by autoclave with certain pressure release speed discharge, polybutene bead spurts into cold water cooling system, Obtain polybutene expanded bead of the expansion ratio between 2-20 times；By the polybutene expanded bead tentatively obtained in second time of foaming In device, in vapor atmosphere, pressure 0.1-1.5MPa is controlled, discharge after 10~60s is kept, further obtains higher hair Multiplying power polybutene expanded bead is steeped, expansion ratio is at 15-60 times.
6) polybutene expanded bead dry 10~48h in 30~60 DEG C of environment is prepared, by the polybutene expanded bead after drying It is injected into vapor compression molding device, by vapor heating, cooling, obtains polybutene expanded bead formed body.
9. according to the method described in claim 8, it is characterized in that, the dispersing agent be kaolin, the basic sodium sulfonate of dodecane, One or more of aluminum sulfate, calcium carbonate, barium sulfate, alumino-silicate.
10. according to the method described in claim 8, it is characterized in that, the physical blowing agent is carbon dioxide, one in nitrogen Kind or two kinds.
11. according to the method described in claim 8, it is characterized in that, the depressurization rate of autoclave is 0.3- in step (5) 2.0MPa/s, polybutene bead-aqueous dispersion mixture cooling rate are 10-25 DEG C/s.
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