WO2018040624A1 - 一种制备热塑性聚合物发泡珠粒的方法 - Google Patents

一种制备热塑性聚合物发泡珠粒的方法 Download PDF

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WO2018040624A1
WO2018040624A1 PCT/CN2017/085479 CN2017085479W WO2018040624A1 WO 2018040624 A1 WO2018040624 A1 WO 2018040624A1 CN 2017085479 W CN2017085479 W CN 2017085479W WO 2018040624 A1 WO2018040624 A1 WO 2018040624A1
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polymer
sealed container
foaming
temperature
expanded beads
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PCT/CN2017/085479
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English (en)
French (fr)
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余加保
唐云
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杭州博适特新材料科技有限公司
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Priority to EP17844931.0A priority Critical patent/EP3508521A4/en
Publication of WO2018040624A1 publication Critical patent/WO2018040624A1/zh

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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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • B29C44/3465—Making or treating expandable particles by compressing particles in vacuum, followed by expansion in normal pressure
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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

Definitions

  • the present invention relates to a method of preparing a thermoplastic polymer foamed material, and more particularly to a method of preparing a high rate thermoplastic polymer expanded bead using a supercritical fluid technique.
  • foaming technology to form a large number of bubbles inside the polymer material to form a porous polymer foam material is an effective means for achieving light weight and material saving.
  • the presence of a large number of cells also gives the material excellent thermal insulation, damping buffer, noise reduction and sound absorption.
  • the higher the expansion ratio of the polymer foamed material the lighter the weight of the product, the more material is saved, and the better the properties such as heat insulation and cushioning.
  • thermosetting foams that are prone to environmental pollution
  • thermoplastic foams that can be recycled and processed have broader application prospects.
  • high-rate foamed products have irregular or even very complex geometries such as automotive parts, packaging protective products, children's toys, sports equipment, water buoys, and the like.
  • thermoplastic polymer foamed products with large size and complicated profiled structure, there is no reliable one-time foaming molding technology.
  • the efficiency is low, the cost is high, and a large amount of corner scraps are generated, resulting in material waste.
  • the two-step molding method of preparing high-strength thermoplastic polymer expanded beads and then welding the surface of the expanded beads through steam in the mold is an effective way to prepare a large-magnification shaped foamed product, and can realize large The high-efficiency production of multi-shaped shaped foamed parts, the production process without corner scraps, and high material utilization rate.
  • the polymer particles are dispersed in water, and the blowing agent gas dissolves and diffuses into the polymer particles under high temperature and high pressure, and then causes rapid venting to initiate nucleation and growth of the bubbles to form expanded beads.
  • the aqueous suspension used consumes a large amount of heat and the heating process also results in a long production cycle.
  • the expanded beads obtained by this method are also washed with water to remove various additives which adhere to the surface from the aqueous suspension to prevent subsequent fusion forming, which again causes waste of water resources and costs. increase.
  • thermoplastic polyurethane TPU
  • PLA polylactic acid
  • Continuous extrusion foaming is also used to make polymer foamed beads. The extrusion foaming process is easy to cause the opening ratio of the bubbles to be high due to the polymer being in a molten state, which causes the foamed bead products to shrink and deform easily. Subsequent welding process.
  • the foaming agent gas is not safe and environmentally friendly; the process energy consumption is high, the product cost is high; the process is complicated, and the production efficiency is low, which is an urgent problem to be solved in the polymer bead foaming industry.
  • thermoplastic polymer expanded beads comprising the following steps:
  • the sealed container is depressurized, the supercritical fluid is discharged, and the nucleation and growth of the cells are induced by controlling the pressure release rate, so that the polymer beads expand and grow;
  • the foaming temperature of the step 1) is a temperature at which the polymer particles can be plastically deformed, but can not flow.
  • the foaming temperature is within the range of Tg to Tg + 40 ° C, and the Tg is an amorphous polymerization.
  • the glass transition temperature of the material; for the crystalline polymer, the foaming temperature is within the range of Tm-20 ° C ⁇ Tm, and Tm is the melting point of the crystalline polymer;
  • the deposition volume of the polymer particles in the sealed container is ⁇ 90% of the volume of the sealed container
  • the supercritical fluid has a pressure of 5-30 MPa
  • the sealed container is selected from an autoclave and installed in a hot press
  • the autoclave includes a kettle body and a kettle lid.
  • the cover is installed on the upper beam of the hot press, and the inlet valve and the exhaust valve are installed on the kettle lid, and the kettle body is mounted on the lower beam of the hot press to move along with the oil cylinder; the kettle lid and the kettle body are mounted thereon.
  • the temperature control element is heated; the sealed space is formed by the enclosure in the hot press, and the vacuum press is connected to the hot press, and the sealed space is vacuumed by the vacuum pump.
  • the amorphous polymer has a foaming temperature within the range of Tg to Tg + 20 °C.
  • the crystalline polymer has a foaming temperature within a range of from Tm to 10 °C to Tm.
  • the polymer particles are selected from the group consisting of polyethylene (PE), polypropylene (PP), and polylactic acid.
  • PE polyethylene
  • PP polypropylene
  • polylactic acid One of (PLA), thermoplastic polyurethane (TPU), block polyether amide elastomer (Pebax), ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), thermoplastic polyester elastomer (TPEE)
  • PVA polyethylene
  • PP polypropylene
  • PP polylactic acid.
  • PPA polyethylene
  • TPU thermoplastic polyurethane
  • Pebax block polyether amide elastomer
  • EVA ethylene-vinyl acetate copolymer
  • POE polyolefin elastomer
  • TPEE thermoplastic polyester elastomer
  • the mixture has a number average molecular weight of 1 to 5,000,000.
  • the polymer particles have a diameter of from 0.2 to 5 mm.
  • the supercritical fluid is supercritical carbon dioxide or supercritical nitrogen or a mixed fluid of any ratio of the two.
  • the invention forms a high temperature and high pressure atmosphere in the autoclave, achieves the balance of heat transfer and mass transfer inside the polymer particles, and then quickly relieves pressure, so that the gas dissolved in the polymer is supersaturated, thereby causing Nucleation and growth of cells.
  • the autoclave is opened, as the particles enter the vacuum environment, the resistance encountered by the cell growth is reduced, and the cells have the opportunity to further grow, thereby forming high-rate polymer expanded beads.
  • the invention has the beneficial effects of using clean supercritical carbon dioxide or supercritical nitrogen technology instead of other various unsafe and environmentally friendly foaming agents, the process is clean and environmentally friendly, the product is clean and pollution-free, the beads do not need to be cleaned after foaming, and the process flow is short .
  • the vacuum technology outside the kettle the resistance encountered by the bubble growth is reduced, the cells have the opportunity to further grow, and the expanded beads are easily realized by the two expanded expanded beads, thereby further reducing the weight of the product, and Saving materials, while helping to reduce energy consumption and improve foaming efficiency. Since the diffusion area of the high-pressure gas inside the particles is large and the diffusion path is short, the diffusion balance can be achieved relatively quickly, and the foaming time is extremely shortened compared to the one-time foam molding of the large-sized product.
  • high-magnification foamed products especially large-sized high-magnification foamed products
  • high-rate foam beads are efficiently obtained by supercritical fluid particle foaming technology, and then steam-surface welding is formed in the mold. It can greatly improve the production efficiency of large-rate foamed products and significantly reduce costs.
  • Fig. 1 is a photograph of the expanded beads obtained in Example 1.
  • Fig. 2 is a scanning photograph of the internal cell morphology of the expanded beads obtained in Example 1.
  • Fig. 3 is a photograph of the expanded beads obtained in Example 2.
  • Fig. 4 is a scanning photograph of the internal cell morphology of the expanded beads obtained in Example 2.
  • Figure 5 is an article obtained by the surface fusion technique of the product of Example 2.
  • Fig. 6 is a schematic view showing the structure of a device for use of the present invention.
  • the analysis test method is as follows:
  • the expanded beads were quenched by liquid nitrogen cooling, and the cross section was sprayed with gold, and the cell structure inside the expanded beads was observed using a scanning electron microscope.
  • the autoclave mounted on the hot press 1 was heated to 105 ° C, and PE particles having an average diameter of 2.3 mm, a number average molecular weight of 150,000, and a melting point of 110 ° C were charged into the autoclave, and the kettle body 2 was raised by the oil cylinder 4
  • the mold was pressed and sealed, and 20 MPa of supercritical CO2 was introduced into the autoclave through the intake valve 5.
  • the vacuum pump 7 is started to cause a vacuum to be formed outside the autoclave in the hot press 1.
  • the exhaust valve 6 is quickly opened to release the CO2 gas pressure of the autoclave, and the cells nucleate and grow inside the PE particles, causing the expansion of the PE particles, and rapidly opening the autoclave through the cylinder 4,
  • the PE particles are ejected from the autoclave into a vacuum environment, and the cells inside the PE particles are further grown, and the particles are further expanded.
  • the foaming properties of the obtained foamed material are shown in Table 1.
  • the autoclave mounted on the hot press 1 was heated to 124 ° C, and PP particles having an average diameter of 3.4 mm, a number average molecular weight of 210,000 and a melting point of 132 ° C were charged into the autoclave, and the kettle body 2 was raised by the oil cylinder 4
  • the mold was pressed and sealed, and 15 MPa of supercritical CO2 was introduced into the autoclave through the intake valve 5.
  • the vacuum pump 7 is started to cause a vacuum to be formed outside the autoclave in the hot press 1.
  • the exhaust valve 6 is quickly opened to release the CO2 gas pressure of the autoclave, and the bubbles nucleate and grow inside the PP particles, causing the expansion of the PP particles, and rapidly opening the autoclave through the cylinder 4, thereby enabling the autoclave to be opened.
  • the bubbles of the PP particles ejected from the autoclave to the inside of the vacuum environment are further grown, and the particles are further expanded.
  • the foaming properties of the obtained foamed material are shown in Table 1.
  • the autoclave mounted on the hot press 1 was heated to 132 ° C, and TPU particles having an average diameter of 4.1 mm, a number average molecular weight of 80,000 and a melting point of 142 ° C were charged into the autoclave, and the kettle body 2 was raised by the oil cylinder 4
  • the mold was pressed and sealed, and 25 MPa of supercritical CO2 was introduced into the autoclave through the intake valve 5.
  • the vacuum pump 7 is started to cause a vacuum to be formed outside the autoclave in the hot press 1.
  • the exhaust valve 6 is quickly opened to release the CO2 gas pressure of the autoclave, and the bubbles nucleate and grow inside the TPU particles, causing the expansion of the TPU particles, and rapidly opening the autoclave through the cylinder 4, thereby enabling the autoclave to be opened.
  • the TPU particles are ejected from the autoclave into a vacuum environment, and the bubbles inside the TPU particles are further grown. The particles expand further.
  • the foaming properties of the obtained foamed material are shown in Table 1.
  • the autoclave mounted on the hot press 1 was heated to 108 ° C, and PLA particles having an average diameter of 3.5 mm, a number average molecular weight of 150,000, and a melting point of 115 ° C were charged into the autoclave, and the kettle body 2 was raised by the oil cylinder 4
  • the mold was pressed and sealed, and 20 MPa of supercritical CO2 was introduced into the autoclave through the intake valve 5.
  • the vacuum pump 7 is started to cause a vacuum to be formed outside the autoclave in the hot press 1.
  • the exhaust valve 6 is quickly opened to release the CO2 gas pressure of the autoclave, and the bubbles nucleate and grow inside the PLA particles, causing the expansion of the PLA particles, and rapidly opening the autoclave through the cylinder 4 to open the autoclave.
  • the PLA particles are ejected from the autoclave into a vacuum environment, and the bubbles inside the PLA particles are further grown, and the particles are further expanded.
  • the foaming properties of the obtained foamed material are shown in Table 1.
  • Table 1 shows the test results of the average pore diameter, particle density, and expansion ratio of the above four examples.
  • the TPU foam beads obtained in Example 3 were added to a mold of a desired shape, the mold was locked, steam was introduced, and steam was passed through a steam plug on the surface of the mold to enter the TPU foam beads, and the steam pressure was applied at 0.18-0.35 bar. Next, the surface of the TPU foam beads is softened and welded, and after being formed, the cooling water is passed to cool the mold. After the mold is cooled, the mold is opened and the product is released from the mold to obtain a TPU molded product.
  • Fig. 5 shows a TPU molded article obtained in Example 5.

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Abstract

本发明公开了一种制备热塑性聚合物发泡珠粒的方法，包括以下步骤：1)将聚合物粒子投入升温至发泡温度的密封容器内，并将密封容器置于真空环境中；2)向密封容器通入超临界流体，进行溶胀扩散；3)待超临界流体溶胀扩散5-60min后，对密封容器进行泄压，排去超临界流体，通过控制泄压速率诱导泡孔的成核与生长，使聚合物珠粒膨胀长大；4)将密封容器内的聚合物珠粒引出至真空环境中进一步膨胀长大，最终得到高发泡倍率的聚合物发泡珠粒；所述的步骤1)的发泡温度为聚合物粒子可发生塑性形变，但还不能流动的温度，对于无定型聚合物，发泡温度在Tg～Tg+40℃之内，Tg为无定形聚合物的玻璃化转变温度；对于结晶聚合物，发泡温度在Tm-20℃～Tm之内，Tm为结晶聚合物的熔点。

Description

一种制备热塑性聚合物发泡珠粒的方法 技术领域
本发明涉及一种制备热塑性聚合物发泡材料的方法，特别涉及一种利用超临界流体技术制备高倍率热塑性聚合物发泡珠粒的方法。
背景技术
利用发泡技术使高分子材料内部形成大量气泡，形成多孔结构的高分子泡沫材料，是实现制品轻量化，节约材料的有效手段。大量泡孔的存在，还赋予材料优良的隔热保温、阻尼缓冲、降噪吸音等特性。一般而言，高分子发泡材料的发泡倍率越高，也就意味着制品重量越轻，越节约材料，同时隔热、缓冲等性能越优异。相对于不可循环利用，易造成环境污染的热固性泡沫材料，可循环加工利用的热塑性泡沫塑料具有更广阔的应用前景。
在大多数的应用场景中，高倍率发泡制品都具有不规则甚至非常复杂的几何形状，如汽车零部件、包装防护制品、儿童玩具、体育器材、水上浮标等。对于制件尺寸较大，具有复杂异形结构的大倍率热塑性聚合物发泡制品，目前还没有可靠的一次性发泡成型技术手段。通过车削加工高倍率挤出发泡板材制造异形发泡制件，效率低，成本高，还会产生大量边角废料，造成材料浪费。而先制备出高倍率的热塑性聚合物发泡珠粒，再通过模具内蒸汽使发泡珠粒表面熔接成型的两步成型法，是制备大倍率异形结构发泡制品的有效途径，可实现大倍率异形发泡制件的高效生产，生产过程无边角废料，材料利用率高。
文献Past and present developments in polymer bead foams and bead foaming technology,polymer,56,(2015)5-19，综述了现有的几种珠粒成型的方法。悬浮聚合时加入发泡剂，形成包含发泡剂的可发泡聚合物粒子，再通过后续的升温发泡形成聚合物发泡珠粒，此种方法仅适用于玻璃化温度(Tg)较高的无定型聚合物，如聚苯乙烯(PS)的珠粒发泡，而不适用于结晶聚合物，且使用的烷烃类发泡剂，如常用的丁烷、戊烷，属于易燃物质。釜压发泡中聚合物粒子分散于水中，发泡剂气体在高温高压下溶解扩散进入聚合物粒子，后通过快速泄压，引发气泡的成核和生长，形成发泡珠粒，此种方法使用的水悬浮液需要消耗大量的热量，加热过程也造成生产周期较长。再者，利用这种方法得到的发泡珠粒还要经过水洗，去除其表面从水悬浮液中粘附的各种助剂，以防止影响后续的熔接成型，再次造成水资源的浪费和成本增加。此外，多种易降解高分子，如热塑性聚氨酯(TPU)、聚乳酸(PLA) 等，也不适合在高温下用水蒸煮较长时间。连续挤出发泡也被用于制造聚合物发泡珠粒，挤出发泡过程由于聚合物处于熔融态，容易造成气泡的开孔率较高，导致发泡珠粒产品容易收缩变形，影响后续的熔接工艺。
发泡剂气体不安全环保；过程能量消耗较多，产品成本较高；制程复杂，生产效率较低，是聚合物珠粒发泡行业亟需解决的问题。
发明内容
为解决现有技术中的不足，本发明的目的是提供一种利用清洁发泡技术高效制备高倍率热塑性聚合物发泡珠粒的方法。
为实现上述目的，本发明的技术方案为：一种制备热塑性聚合物发泡珠粒的方法，包括以下步骤：
1)将聚合物粒子投入升温至发泡温度的密封容器内，并将密封容器置于真空环境中；
2)向密封容器通入超临界流体，进行溶胀扩散；
3)待超临界流体溶胀扩散5-60min后，对密封容器进行泄压，排去超临界流体，通过控制泄压速率诱导泡孔的成核与生长，使聚合物珠粒膨胀长大；
4)将密封容器内的聚合物珠粒引出至真空环境中进一步膨胀长大，最终得到高发泡倍率的聚合物发泡珠粒；
所述的步骤1)的发泡温度为聚合物粒子可发生塑性形变，但还不能流动的温度，对于无定型聚合物，发泡温度在Tg～Tg+40℃之内，Tg为无定形聚合物的玻璃化转变温度；对于结晶聚合物，发泡温度在Tm-20℃～Tm之内，Tm为结晶聚合物的熔点；
所述的聚合物粒子在密封容器内的堆积体积≤密封容器体积的90％；
所述的超临界流体的压力为5-30MPa；
为了减少热量损失、降低整个流程的能耗，提高发泡效率与发泡效果，所述的密封容器选用高压釜并安装于热压机内，所述的高压釜包括釜体与釜盖，釜盖安装于热压机的上梁，釜盖上安装有进气阀与排气阀，釜体安装于热压机下梁可随油缸一起移动；所述的釜盖与釜体上均安装有加热控温元件；所述的热压机内通过围板形成密闭空间，热压机连接有真空泵，通过真空泵将密闭空间形成真空。
作为优选，所述的无定型聚合物的发泡温度在Tg～Tg+20℃之内。
作为优选，所述的结晶聚合物的发泡温度在Tm-10℃～Tm之内。
作为优选，所述的聚合物粒子选自聚乙烯(PE)、聚丙烯(PP)、聚乳酸 (PLA)、热塑性聚氨酯(TPU)、嵌段聚醚酰胺弹性体(Pebax)、乙烯-醋酸乙烯共聚物(EVA)、聚烯烃弹性体(POE)、热塑性聚酯弹性体(TPEE)中的一种或多种组合，数均分子量为1～500万。
作为优选，所述的聚合物粒子直径为0.2-5mm。
作为优选，所述的超临界流体为超临界二氧化碳或超临界氮气或二者的任一比例的混合流体。
本发明的技术原理：本发明通过在高压釜内形成高温高压气氛，使聚合物粒子内部达到传热和传质的平衡，然后快速泄压，使溶解在聚合物内部的气体过饱和，从而引发泡孔的成核和生长。开釜后，由于粒子进入真空环境，泡孔生长遇到的阻力减小，泡孔有机会进一步生长，从而形成高倍率的聚合物发泡珠粒。
本发明的有益效果：使用清洁的超临界二氧化碳或超临界氮气技术，代替其他各种不安全环保的发泡剂，过程清洁环保，制品清洁无污染，发泡后珠粒无需清洗，工艺流程短。通过釜外真空技术，使气泡生长遇到的阻力减小，泡孔得以有机会进一步长大，经过两次膨胀的发泡珠粒容易实现更大的发泡倍率，从而进一步降低制品重量，并节约材料，同时有利于降低能耗，提高发泡效率。由于高压气体在粒子内部的扩散面积大，扩散路径短，可以较快地实现扩散平衡，相对于大尺寸产品的一次性发泡成型，发泡时间极大缩短。因此对于高倍率的发泡制品，尤其是大尺寸的高倍率发泡制品而言，首先通过超临界流体粒子发泡技术，高效得到高倍率发泡珠粒，再通过模具内蒸汽表面熔接成型，可大幅提高大倍率发泡制品的生产效率，并显著降低成本。
附图说明
图1为实施例1得到的发泡珠粒的照片。
图2为实施例1得到的发泡珠粒的内部泡孔形态的扫描照片。
图3为实施例2得到的发泡珠粒的照片。
图4为实施例2得到的发泡珠粒的内部泡孔形态的扫描照片。
图5为实施例2的产品通过表面熔接技术得到的制品。
图6为本发明的使用装置的结构示意图。
具体实施方式
分析测试方式如下：
使用梅特勒-托利多带密度组件的XSE分析天平，测得发泡珠粒的密度，计算得到发泡珠粒的体积膨胀倍率，体积膨胀倍率(Rex)＝ρpolymer/ρfoam，其中，ρpolymer为原粒子的密度，ρfoam为发泡珠粒的密度。将发泡珠粒经液氮冷却淬断，断面喷金，使用扫描电子显微镜观察发泡珠粒内部的泡孔结构。
实施例1
将安装在热压机1上的高压釜升温至105℃，向高压釜内投入平均直径为2.3mm，数均分子量为15万，熔点为110℃的PE粒子，釜体2通过油缸4上升合模并施压密封，通过进气阀5向高压釜内通入20MPa的超临界CO2。同时启动真空泵7，使热压机1内高压釜外部形成真空。CO2向PP粒子内扩散20min后，快速打开排气阀6，释放高压釜的CO2气压，泡孔在PE粒子内部成核并生长，引发PE粒子的膨胀，并通过油缸4迅速下降打开高压釜，使PE粒子从高压釜内弹出至真空环境中，PE粒子内部的泡孔进一步长大，粒子进一步膨胀。得到的发泡材料的发泡性能见表1。
实施例2
将安装在热压机1上的高压釜升温至124℃，向高压釜内投入平均直径为3.4mm，数均分子量为21万，熔点为132℃的PP粒子，釜体2通过油缸4上升合模并施压密封，通过进气阀5向高压釜内通入15MPa的超临界CO2。同时启动真空泵7，使热压机1内高压釜外部形成真空。CO2向PP粒子内扩散30min后，快速打开排气阀6，释放高压釜的CO2气压，气泡在PP粒子内部成核并生长，引发PP粒子的膨胀，并通过油缸4迅速下降打开高压釜，使PP粒子从高压釜内弹出至真空环境中内部的气泡进一步长大，粒子进一步膨胀。得到的发泡材料的发泡性能见表1。
实施例3
将安装在热压机1上的高压釜升温至132℃，向高压釜内投入平均直径为4.1mm，数均分子量为8万，熔点为142℃的TPU粒子，釜体2通过油缸4上升合模并施压密封，通过进气阀5向高压釜内通入25MPa的超临界CO2。同时启动真空泵7，使热压机1内高压釜外部形成真空。CO2向PE粒子内扩散10min后，快速打开排气阀6，释放高压釜的CO2气压，气泡在TPU粒子内部成核并生长，引发TPU粒子的膨胀，并通过油缸4迅速下降打开高压釜，使TPU粒子从高压釜内弹出至真空环境中，TPU粒子内部的气泡进一步长大， 粒子进一步膨胀。得到的发泡材料的发泡性能见表1。
实施例4
将安装在热压机1上的高压釜升温至108℃，向高压釜内投入平均直径为3.5mm，数均分子量为15万，熔点为115℃的PLA粒子，釜体2通过油缸4上升合模并施压密封，通过进气阀5向高压釜内通入20MPa的超临界CO2。同时启动真空泵7，使热压机1内高压釜外部形成真空。CO2向PLA粒子内扩散20min后，快速打开排气阀6，释放高压釜的CO2气压，气泡在PLA粒子内部成核并生长，引发PLA粒子的膨胀，并通过油缸4迅速下降打开高压釜，使PLA粒子从高压釜内弹出至真空环境中，PLA粒子内部的气泡进一步长大，粒子进一步膨胀。得到的发泡材料的发泡性能见表1。
表1 为上述四个实施例的平均孔径、粒子密度和发泡倍率的测试结果。
Figure PCTCN2017085479-appb-000001
实施例5
模具成型
将实施例3得到的TPU发泡珠粒加入到所需要形状的模具中，锁紧模具，加入蒸汽，蒸汽通过模具表面的汽塞进入TPU发泡珠粒，在0.18-0.35bar的蒸汽压力作用下，TPU发泡珠粒表面软化并熔接，待其成型后，通入冷却水冷却模具，模具冷却完成后，开模并将产品脱离模具，得到TPU模制品。图5为实施例5得到TPU模压制品。
除上述优选实施例外，本发明还有其他的实施方式，本领域技术人员可以根据本发明作出各种改变和变形，只要不脱离本发明的精神，均应属于本发明所附权利要求所定义的范围。

Claims (7)

  1. 一种制备热塑性聚合物发泡珠粒的方法，其特征在于，包括以下步骤：1)将聚合物粒子投入升温至发泡温度的密封容器内，并将密封容器置于真空环境中；2)向密封容器通入超临界流体，进行溶胀扩散；3)待超临界流体溶胀扩散5-60min后，对密封容器进行泄压，排去超临界流体，通过控制泄压速率诱导泡孔的成核与生长，使聚合物珠粒膨胀长大；4)将密封容器内的聚合物珠粒引出至真空环境中进一步膨胀长大，最终得到高发泡倍率的聚合物发泡珠粒；所述的步骤1)的发泡温度为聚合物粒子可发生塑性形变，但还不能流动的温度，对于无定型聚合物，发泡温度在Tg～Tg+40℃之内，Tg为无定形聚合物的玻璃化转变温度；对于结晶聚合物，发泡温度在Tm-20℃～Tm之内，Tm为结晶聚合物的熔点；所述的聚合物粒子在密封容器内的堆积体积≤密封容器体积的90％；所述的超临界流体的压力为5-30MPa；对于不同种类的聚合物，在上述条件下得到的聚合物发泡珠粒体积膨胀倍率为1～80倍，发泡珠粒直径为：0.5-22mm。
  2. 根据权利要求1所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的密封容器选用高压釜并安装于热压机(1)内，所述的高压釜包括釜体(2)与釜盖(3)，釜盖(3)安装于热压机(1)的上梁，釜盖(3)上安装有进气阀(5)与排气阀(6)，釜体(2)安装于热压机(1)下梁并随油缸(4)一起移动；所述的釜盖(3)与釜体(2)上均安装有加热控温元件(8)；所述的热压机(1)内通过围板形成密闭空间，热压机(1)连接有真空泵(7)，通过真空泵(7)将密闭空间形成真空。
  3. 根据权利要求1所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的无定型聚合物的发泡温度在Tg～Tg+20℃之内。
  4. 根据权利要求1所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的结晶聚合物的发泡温度在Tm-10℃～Tm之内。
  5. 根据权利要求1所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的聚合物粒子选自聚乙烯(PE)、聚丙烯(PP)、聚乳酸(PLA)、热塑性聚氨酯(TPU)、嵌段聚醚酰胺弹性体(Pebax)、乙烯-醋酸乙烯共聚物(EVA)、聚烯烃弹性体(POE)、热塑性聚酯弹性体(TPEE)中的一种或多种组合，数均分子量为1～500万。
  6. 根据权利要求1或5所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的聚合物粒子直径为0.2-5mm。
  7. 根据权利要求1所述的一种制备热塑性聚合物发泡珠粒的方法，其特征在于，所述的超临界流体为超临界二氧化碳或超临界氮气或二者的任一比例的 混合流体。
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