WO2019085158A1 - 具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法 - Google Patents

具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法 Download PDF

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WO2019085158A1
WO2019085158A1 PCT/CN2017/115520 CN2017115520W WO2019085158A1 WO 2019085158 A1 WO2019085158 A1 WO 2019085158A1 CN 2017115520 W CN2017115520 W CN 2017115520W WO 2019085158 A1 WO2019085158 A1 WO 2019085158A1
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particles
blended
polyether amide
sandbag structure
preparing
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PCT/CN2017/115520
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English (en)
French (fr)
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顾飚
董卫龙
夏洋
巢雄飞
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常州市顺祥新材料科技股份有限公司
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Priority to EP17917218.4A priority Critical patent/EP3517574A4/en
Priority to KR1020197023864A priority patent/KR102263684B1/ko
Priority to JP2019527498A priority patent/JP6852921B2/ja
Priority to US16/469,974 priority patent/US11124619B2/en
Publication of WO2019085158A1 publication Critical patent/WO2019085158A1/zh

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    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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Definitions

  • the invention relates to the field of foaming materials, in particular to a preparation method of a block polyetheramide foaming particle having a sandbag structure.
  • a block polyether amide foam material is generally prepared by organic chemical foaming.
  • the preparation process has two disadvantages: 1. Although the use of a crosslinking agent can partially improve the physical properties of the product, the crosslinking agent can make the preparation. The product can not be recycled again and waste resources; Second, the mixing of organic chemical foaming is blended with the block polyether amide by a kneading machine. On the one hand, the mixing of solid and solid cannot achieve a homogeneous system, so that The uniformity of foaming in each place is not guaranteed. On the other hand, the presence of the organic foaming agent remaining after foaming has a great influence on the properties of the product.
  • an object of the present invention is to provide a method for preparing a high performance sandbag structure block polyetheramide expanded particle by a modifier and an environmentally friendly physical foaming agent.
  • a preparation method of a polystyrene amide expanded particle having a sandbag structure characterized in that the method comprises the following steps:
  • the modifier, the filler, the coupling agent are premixed, and the premixed raw materials are melt blended, and the blended particles I having a core-shell structure are prepared by underwater granulation or sink granulation;
  • step S2 premixing the blended particles I prepared in step S1 with the block polyetheramide raw materials, and then premixing After the raw material is melt blended, and the block polyether amide blending particles II having a sandbag structure are obtained by underwater granulation or sink cutting;
  • the quantitatively blended particles II are put into the autoclave, the autoclave is adjusted to a certain temperature and kept at a constant temperature, and then a quantitative environmentally friendly physical foaming agent is introduced, after a certain penetration time until the foaming agent and the G2 blended particles After reaching the homogeneous system, the pressure in the kettle is evacuated through a pressure relief valve, and the block polyetheramide blending particles III containing the blowing agent are taken out;
  • the blended particles III prepared in the step S3 are transferred into a constant temperature device which has been raised to the softening temperature of the particles, and after a period of holding time, the block polyetheramide expanded particles having a sandbag structure can be obtained.
  • the modifier is 2 to 15 parts
  • the filler is 1 to 5 parts
  • the coupling agent is 0.003 to 0.1 parts
  • the block polyether amide is 100 parts
  • the environmentally friendly physical foaming agent is 10 to 60 servings.
  • the modifier is thermoplastic polyurethane, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, EPDM One or more
  • the filler is one or more of calcium carbonate, talc, kaolin, silica or barium sulfate;
  • the coupling agent is any one of a silane coupling agent and a titanate coupling agent or a mixture thereof;
  • the block polyether amide has a Shore D20-60 hardness.
  • the environmentally friendly physical blowing agent is one or more of carbon dioxide, nitrogen, high pressure air, and argon.
  • the autoclave temperature is 35-60 ° C
  • the pressure is 4-24 MPa
  • the permeation time is 0.5-8 hours
  • the pressure relief emptying time is 20-60 seconds.
  • the constant temperature device is a blast dryer, a fluidized bed, an oil bath or a steam-receiving reaction kettle, and the temperature of the constant temperature device is 100-200 ° C, and the constant temperature time is 5-60 seconds. .
  • the premixing is performed in a dispersing machine, and the melt blending is performed in an extruder.
  • the filler is a core and the modifier is a shell.
  • the obtained polyetheramide blended particles having a sandbag structure have a single weight of 4-50 mg and an aspect ratio of 5:1.
  • the obtained polyetheramide expanded particles having a sandbag structure have a density of 0.01-0.5 g/cm3, a single particle weight of 4-50 mg, and an aspect ratio of 5:1.
  • the content of the foaming agent is from 0.5% to 20%.
  • the present invention has at least the following advantages:
  • the foaming agents used in the present invention are all environmentally friendly foaming agents, and there is no pollution to the environment;
  • the sandbag structure block polyetheramide foamed particles obtained by the method of the present invention have higher impact strength and toughness than other foam materials due to the sandbag structure, and the permanent deformation is also reduced.
  • the block polyether amide foam product prepared by the method of the invention has better resilience performance than any foam product on the market, and can reach up to 85%;
  • the filler is added to the block polyether amide foam material of the present invention, on the one hand, the mechanical properties of the foam material can be improved, and on the other hand, the material cost can be reduced;
  • the foam material prepared by the present invention does not crosslink at all, and can be further subjected to melt recovery to reduce the generation of environmental waste.
  • the block polyether amide foam product prepared by the method of the invention can be adjusted at a density of 0.01-0.5 g/cm3, and the density can be controlled.
  • Figure 1 is a scanning electron micrograph (SEM) of a block polyetheramide foamed particle of the sandbag structure of the present invention.
  • a preparation method of a block polyetheramide foamed particle having a sandbag structure comprising the following steps:
  • the modifier, the filler, the coupling agent are premixed, and the premixed raw materials are melt blended, and the blended particles I having a core-shell structure are prepared by underwater granulation or sink granulation;
  • step S2 pre-mixing the blended particles I prepared in step S1 with the block polyetheramide raw materials, and then melt-blending the pre-mixed raw materials, and forming the sandbag structure by underwater granulation or sink cutting.
  • the quantitatively blended particles II are put into the autoclave, the autoclave is adjusted to a certain temperature and kept at a constant temperature, and then a quantitative environmentally friendly physical foaming agent is introduced, after a certain penetration time until the foaming agent and the G2 blended particles After the homogeneous system is reached, the pressure in the autoclave is evacuated through a pressure relief valve, and the block polyetheramide blending particles III containing the blowing agent are taken out.
  • the blended particles III prepared in the step S3 are transferred into a constant temperature device which has been raised to the softening temperature of the particles, and after a period of holding time, the block polyetheramide expanded particles having a sandbag structure can be obtained.
  • the modifier is 2 to 15 parts
  • the filler is 1 to 5 parts
  • the coupling agent is 0.003 to 0.1 parts
  • the block polyether amide is 100 parts
  • the environmentally friendly physical foaming agent is 10 to 60 servings.
  • the modifier is thermoplastic polyurethane, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, EPDM One or more
  • the filler is one or more of calcium carbonate, talc, kaolin, silica or barium sulfate;
  • the coupling agent is any one of a silane coupling agent and a titanate coupling agent or a mixture thereof;
  • the block polyether amide has a Shore D20-60 hardness.
  • the environmentally friendly physical blowing agent is one or more of carbon dioxide, nitrogen, high pressure air, and argon.
  • the autoclave temperature is 35-60 ° C
  • the pressure is 4-24 MPa
  • the permeation time is 0.5-8 hours
  • the pressure relief emptying time is 20-60 seconds.
  • the constant temperature device is a blast dryer, a fluidized bed, an oil bath or a steam-receiving reaction kettle, and the temperature of the constant temperature device is 100-200 ° C, and the constant temperature time is 5-60 seconds. .
  • the premixing is performed in a dispersing machine, and the melt blending is performed in an extruder.
  • the filler is a core and the modifier is a shell.
  • the obtained polyetheramide blended particles having a sandbag structure have a single weight of 4-50 mg and an aspect ratio of 5:1.
  • the obtained polyetheramide expanded particles having a sandbag structure have a density of 0.01-0.5 g/cm3, a single particle weight of 4-50 mg, and an aspect ratio of 5:1.
  • the content of the foaming agent is from 0.5% to 20%.
  • the present invention is embodied as follows:
  • blended particles I60kg prepared above are pre-mixed with 1000kg of block polyether amide, and then melt blended by an extruder, and the material is cut underwater to obtain a single particle weight of 18 mg, an aspect ratio of 2, and a sandbag.
  • the above 500 kg of the blended particles III were transferred into a vibrating fluidized bed which had been heated to 174 ° C for 60 seconds to obtain a block polyetheramide spindle shaped hair having a density of 0.14 g/cm 3 and an aspect ratio of 2 and having a sandbag structure. Bubble particles.
  • EPDM 150kg EPDM, 10kg calcium carbonate and 0.2kg LK-132 titanate coupling agent were pre-mixed in a dispersing machine, and then melt-blended by a twin-screw granulator to obtain core-shell structure blending particles I154kg.
  • blended particles I154kg prepared above are pre-mixed with 1000kg of block polyether amide, and then melt blended by an extruder, and cut under water to obtain a single particle weight of 4 mg, an aspect ratio of 1, and a sandbag.
  • the structure of the block polyetheramide spherical blended particles II 1150kg.
  • the above 500 kg of the blended particles III was transferred into a vibrating fluidized bed which had been heated to 200 ° C for 60 seconds to obtain a block polyetheramide spherical foam having a density of 0.01 g/cm 3 and an aspect ratio of 1. particle.
  • blended particles I118kg prepared above are pre-mixed with 1000kg of block polyether amide, and then melt blended by an extruder, and cut under water to obtain a single particle weight of 50 mg, an aspect ratio of 5, and a sandbag.
  • the structure of the block polyetheramide spindle-shaped blended particles II1110kg.
  • the above 500 kg of the blended particles III was transferred into a blast drying oven which had been heated to 100 ° C, and kept at a constant temperature for 30 seconds to obtain a block polyetheramide spindle-shaped hair having a density of 0.5 g/cm 3 and an aspect ratio of 5 and having a sandbag structure. Bubble particles.
  • the foaming agents used in the present invention are all environmentally friendly foaming agents, and there is no pollution to the environment;
  • the sandbag structure block polyetheramide foamed particles obtained by the method of the present invention have higher impact strength and toughness than other foam materials due to the sandbag structure, and the permanent deformation is also reduced.
  • the block polyether amide foam product prepared by the method of the invention has better resilience performance than any foam product on the market, and can reach up to 85%;
  • the filler is added to the block polyether amide foam material of the present invention, on the one hand, the mechanical properties of the foam material can be improved, and on the other hand, the material cost can be reduced;
  • the foam material prepared by the present invention does not crosslink at all, and can be further subjected to melt recovery to reduce the generation of environmental waste.
  • the block polyether amide foam product prepared by the method of the invention can be adjusted at a density of 0.01-0.5 g/cm3, and the density can be controlled.

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

Abstract

一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，包括以下步骤：S1、将改性剂、填料、偶联剂预混，再将预混后的原料熔融共混，经水下造粒或水槽切粒后制备出具有核壳结构的共混粒子Ⅰ；S2、将共混粒子Ⅰ与嵌段聚醚酰胺原料预混，再将预混后的原料熔融共混，经水下造粒或水槽切料后制得具有沙袋结构的嵌段聚醚酰胺共混粒子Ⅱ；S3、将定量共混粒子Ⅱ投入高压釜内，再通入定量的环境友好物理发泡剂，直到发泡剂与G2共混粒子达到均相体系后，再通过泄压阀将釜内的压力排空，取出含有发泡剂的嵌段聚醚酰胺共混粒子Ⅲ；S4、将共混粒子Ⅲ移入已升至该粒子软化温度的恒温设备中，保温后得到具有沙袋结构的嵌段聚醚酰胺发泡粒子。

Description

[根据细则37.2由ISA制定的发明名称]　具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法 技术领域
本发明涉及发泡材料领域，具体涉及一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法。
背景技术
现有技术中一般通过有机化学发泡来制备嵌段聚醚酰胺泡沫材料，该制备工艺有两个缺点：一、使用交联剂虽然可以部分提高制品的物理性能，但交联剂会使得制备出的产品无法进行再次回收利用，浪费资源；二、有机化学发泡的混入是利用捏合机与嵌段聚醚酰胺进行共混，一方面固体与固体的混合不可能达到均相的体系，使得每个地方发泡均匀性得不到保证，另外一方面，发泡后存留的有机发泡剂的存在对制品的性能有很大的影响。
有鉴于上述的缺陷，本设计人，积极加以研究创新，以期创设一种新型具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，使其更具有产业上的利用价值。
发明内容
为解决上述技术问题，本发明的目的是提供一种通过改性剂和环境友好的物理发泡剂，制备出高性能的沙袋结构嵌段聚醚酰胺发泡粒子的方法。
本发明的技术方案如下：
一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于，包括以下步骤：
S1、将改性剂、填料、偶联剂预混，再将预混后的原料熔融共混，经水下造粒或水槽切粒后制备出具有核壳结构的共混粒子Ⅰ；
S2、将步骤S1制备得到的共混粒子Ⅰ与嵌段聚醚酰胺原料预混，再将预混 后的原料熔融共混，经水下造粒或水槽切料后制得具有沙袋结构的嵌段聚醚酰胺共混粒子Ⅱ；
S3、将定量共混粒子Ⅱ投入高压釜内，高压釜调至一定的温度并保持恒温，再通入定量的环境友好物理发泡剂，经一定的渗透时间直到发泡剂与G2共混粒子达到均相体系后，再通过泄压阀将釜内的压力排空，取出含有发泡剂的嵌段聚醚酰胺共混粒子Ⅲ；
S4、将步骤S3制得的共混粒子Ⅲ移入已升至该粒子软化温度的恒温设备中，经一段保温时间后，可得到具有沙袋结构的嵌段聚醚酰胺发泡粒子。
进一步的，按照重量份数计，改性剂为2～15份、填料为1～5份、偶联剂为0.003～0.1份、嵌段聚醚酰胺为100份、环境友好物理发泡剂为10～60份。
进一步的，所述改性剂为热塑性聚氨酯、高冲击聚苯乙烯、丙烯晴-丁二烯-苯乙烯共聚物、低密度聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、三元乙丙中的一种或多种；
所述填料为碳酸钙、滑石粉、高岭土、二氧化硅或硫酸钡当中的一种或多种；
所述偶联剂为硅烷偶联剂和钛酸酯偶联剂当中的任一种或其混合物；
所述嵌段聚醚酰胺的硬度为邵氏D20-60。
所述环境友好的物理发泡剂为二氧化碳、氮气、高压空气、氩气当中的一种或多种。
进一步的，所述步骤3中，所述高压釜温度为35-60℃，压力为4-24Mpa，渗透时间为0.5-8小时，泄压排空时间为20-60秒。
进一步的，所述步骤S4中，恒温设备为鼓风干燥机、流化床、油浴锅或可通入蒸汽的反应釜，恒温设备的温度为100-200℃，恒温时间为5-60秒。
进一步的，所述步骤S1和S2中，预混均在分散机中进行，熔融共混均在挤出机中进行。
进一步的，所述共混粒子Ⅰ中，填料为核，改性剂为壳。
进一步的，所述步骤2中，得到的具有沙袋结构嵌段聚醚酰胺共混粒子单颗重量为4-50mg，长径比为5：1。
进一步的，所述步骤4中，得到的具有沙袋结构嵌段聚醚酰胺发泡粒子，密度为0.01-0.5g/cm3，单颗粒子重量在4-50mg，长径比为5：1。
进一步的，所述共混粒子Ⅲ中，发泡剂的含量为0.5％-20％。
借由上述方案，本发明至少具有以下优点：
(1)本发明所使用的发泡剂全部是环境友好的发泡剂，对环境不存在污染；
(2)本发明所述的方法制得的具有沙袋结构嵌段聚醚酰胺发泡粒子，因其存在沙袋结构，拥有比其他泡沫材料更高的冲击强度和韧性，永久变形也会缩小。
(3)本发明所述方法制备的嵌段聚醚酰胺泡沫制品，回弹性能优于市场上的任何一款泡沫制品，最高可达到85％；
(4)本发明所述的嵌段聚醚酰胺泡沫材料里添加了填料，一方面可提高泡沫材料的力学性能，另一方面可减小材料成本；
(5)本发明所制备的泡沫材料全部未发生交联，可再次进行熔融回收，减小环境废物的产生。
(6)用本发明所述的方法制备得到的嵌段聚醚酰胺泡沫制品，密度从0.01-0.5g/cm3都可随意调整，密度可控。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附 图详细说明如后。
附图说明
图1本发明沙袋结构的嵌段聚醚酰胺发泡粒子扫描电镜图(SEM)。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
本发明的技术方案如下：
一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，包括以下步骤：
S1、将改性剂、填料、偶联剂预混，再将预混后的原料熔融共混，经水下造粒或水槽切粒后制备出具有核壳结构的共混粒子Ⅰ；
S2、将步骤S1制备得到的共混粒子Ⅰ与嵌段聚醚酰胺原料预混，再将预混后的原料熔融共混，经水下造粒或水槽切料后制得具有沙袋结构的嵌段聚醚酰胺共混粒子Ⅱ；
S3、将定量共混粒子Ⅱ投入高压釜内，高压釜调至一定的温度并保持恒温，再通入定量的环境友好物理发泡剂，经一定的渗透时间直到发泡剂与G2共混粒子达到均相体系后，再通过泄压阀将釜内的压力排空，取出含有发泡剂的嵌段聚醚酰胺共混粒子Ⅲ。
S4、将步骤S3制得的共混粒子Ⅲ移入已升至该粒子软化温度的恒温设备中，经一段保温时间后，可得到具有沙袋结构的嵌段聚醚酰胺发泡粒子。
进一步的，按照重量份数计，改性剂为2～15份、填料为1～5份、偶联剂为0.003～0.1份、嵌段聚醚酰胺为100份、环境友好物理发泡剂为10～60份。
进一步的，所述改性剂为热塑性聚氨酯、高冲击聚苯乙烯、丙烯晴-丁二烯-苯乙烯共聚物、低密度聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、三元乙丙中的一种或多种；
所述填料为碳酸钙、滑石粉、高岭土、二氧化硅或硫酸钡当中的一种或多种；
所述偶联剂为硅烷偶联剂和钛酸酯偶联剂当中的任一种或其混合物；
所述嵌段聚醚酰胺的硬度为邵氏D20-60。
所述环境友好的物理发泡剂为二氧化碳、氮气、高压空气、氩气当中的一种或多种。
进一步的，所述步骤3中，所述高压釜温度为35-60℃，压力为4-24Mpa，渗透时间为0.5-8小时，泄压排空时间为20-60秒。
进一步的，所述步骤S4中，恒温设备为鼓风干燥机、流化床、油浴锅或可通入蒸汽的反应釜，恒温设备的温度为100-200℃，恒温时间为5-60秒。
进一步的，所述步骤S1和S2中，预混均在分散机中进行，熔融共混均在挤出机中进行。
进一步的，所述共混粒子Ⅰ中，填料为核，改性剂为壳。
进一步的，所述步骤2中，得到的具有沙袋结构嵌段聚醚酰胺共混粒子单颗重量为4-50mg，长径比为5：1。
进一步的，所述步骤4中，得到的具有沙袋结构嵌段聚醚酰胺发泡粒子，密度为0.01-0.5g/cm3，单颗粒子重量在4-50mg，长径比为5：1。
进一步的，所述共混粒子Ⅲ中，发泡剂的含量为0.5％-20％。
本发明实施例如下：
实施例1
将20kgTPU、50kg滑石粉与0.15kg的KH550硅烷偶联剂在分散机内预混，再经双螺杆造粒机熔融共混制得核壳结构共混粒子Ⅰ60kg。
再将上述制备得到的共混粒子Ⅰ60kg与1000kg的嵌段聚醚酰胺预混，再经挤出机熔融共混，水下切料，制得单颗粒重为18mg，长径比为2，具有沙袋结构的嵌段聚醚酰胺纺锤形共混粒子Ⅱ1030kg。
称取500kg共混粒子Ⅱ投入高压釜内，高压釜温度恒定为35℃，通入250kg二氧化碳和50kg氩气，压力达到24MPa，在高压釜内恒温0.5小时，待渗透达到平衡时，用泄压阀在20秒规定时间，排空釜内的全部压力，取出发泡剂含量 为10％的共混粒子Ⅲ500kg。
将上述的500kg共混粒子Ⅲ移入已升温至174℃振动流化床内，恒温60秒，得到密度为0.14g/cm3，长径比为2，具有沙袋结构的嵌段聚醚酰胺纺锤形发泡粒子。
实施例2：
将150kgEPDM、10kg碳酸钙与0.2kg的LK-132钛酸酯偶联剂在分散机内预混，再经双螺杆造粒机熔融共混制得核壳结构共混粒子Ⅰ154kg。
再将上述制备得到的共混粒子Ⅰ154kg与1000kg的嵌段聚醚酰胺预混，再经挤出机熔融共混，水下切料，制得单颗粒重为4mg，长径比为1，具有沙袋结构的嵌段聚醚酰胺球形共混粒子Ⅱ1150kg。
称取500kg共混粒子Ⅱ投入高压釜内，高压釜温度恒定为60℃，通入250kg二氧化碳和50kg氮气，压力达到24MPa，在高压釜内恒温8小时，待渗透达到平衡时，用泄压阀在60秒规定时间，排空釜内的全部压力，取出发泡剂含量为20％的共混粒子Ⅲ500kg。
将上述的500kg共混粒子Ⅲ移入已升温至200℃振动流化床内，恒温60秒，得到密度为0.01g/cm3，长径比为1，具有沙袋结构的嵌段聚醚酰胺球形发泡粒子。
实施例3：
将100kgLDPE、20kg二氧化硅与0.2kg的KH570硅烷偶联剂在分散机内预混，再经双螺杆造粒机熔融共混制得核壳结构共混粒子Ⅰ118kg。
再将上述制备得到的共混粒子Ⅰ118kg与1000kg的嵌段聚醚酰胺预混，再经挤出机熔融共混，水下切料，制得单颗粒重为50mg，长径比为5，具有沙袋结构的嵌段聚醚酰胺纺锤形共混粒子Ⅱ1110kg。
称取500kg共混粒子Ⅱ投入高压釜内，高压釜温度恒定为50℃，通入50kg 二氧化碳，压力达到4MPa，在高压釜内恒温0.5小时，待渗透达到平衡时，用泄压阀在30秒规定时间，排空釜内的全部压力，取出发泡剂含量为0.5％的共混粒子Ⅲ500kg。
将上述的500kg共混粒子Ⅲ移入已升温至100℃鼓风干燥箱内，恒温30秒，得到密度为0.5g/cm3，长径比为5，具有沙袋结构的嵌段聚醚酰胺纺锤形发泡粒子。
本发明至少具有以下优点：
(1)本发明所使用的发泡剂全部是环境友好的发泡剂，对环境不存在污染；
(2)本发明所述的方法制得的具有沙袋结构嵌段聚醚酰胺发泡粒子，因其存在沙袋结构，拥有比其他泡沫材料更高的冲击强度和韧性，永久变形也会缩小。
(3)本发明所述方法制备的嵌段聚醚酰胺泡沫制品，回弹性能优于市场上的任何一款泡沫制品，最高可达到85％；
(4)本发明所述的嵌段聚醚酰胺泡沫材料里添加了填料，一方面可提高泡沫材料的力学性能，另一方面可减小材料成本；
(5)本发明所制备的泡沫材料全部未发生交联，可再次进行熔融回收，减小环境废物的产生。
(6)用本发明所述的方法制备得到的嵌段聚醚酰胺泡沫制品，密度从0.01-0.5g/cm3都可随意调整，密度可控。
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于，包括以下步骤：
    S1、将改性剂、填料、偶联剂预混，再将预混后的原料熔融共混，经水下造粒或水槽切粒后制备出具有核壳结构的共混粒子Ⅰ；
    S2、将步骤S1制备得到的共混粒子Ⅰ与嵌段聚醚酰胺原料预混，再将预混后的原料熔融共混，经水下造粒或水槽切料后制得具有沙袋结构的嵌段聚醚酰胺共混粒子Ⅱ；
    S3、将定量共混粒子Ⅱ投入高压釜内，高压釜调至一定的温度并保持恒温，再通入定量的环境友好物理发泡剂，经一定的渗透时间直到发泡剂与G2共混粒子达到均相体系后，再通过泄压阀将釜内的压力排空，取出含有发泡剂的嵌段聚醚酰胺共混粒子Ⅲ；
    S4、将步骤S3制得的共混粒子Ⅲ移入已升至该粒子软化温度的恒温设备中，经一段保温时间后，可得到具有沙袋结构的嵌段聚醚酰胺发泡粒子。
  2. 根据权利要求1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：
    按照重量份数计，
    改性剂为2～15份、填料为1～5份、偶联剂为0.003～0.1份、嵌段聚醚酰胺为100份、环境友好物理发泡剂为10～60份。
  3. 根据权利要求2所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：
    所述改性剂为热塑性聚氨酯、高冲击聚苯乙烯、丙烯晴-丁二烯-苯乙烯共聚物、低密度聚乙烯、聚丙烯、乙烯-醋酸乙烯共聚物、三元乙丙中的一种或多种；
    所述填料为碳酸钙、滑石粉、高岭土、二氧化硅或硫酸钡当中的一种或多种；
    所述偶联剂为硅烷偶联剂和钛酸酯偶联剂当中的任一种或其混合物；
    所述嵌段聚醚酰胺的硬度为邵氏D20-60。
    所述环境友好的物理发泡剂为二氧化碳、氮气、高压空气、氩气当中的一种或多种。
  4. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述步骤3中，所述高压釜温度为35-60℃，压力为4-24Mpa，渗透时间为0.5-8小时，泄压排空时间为20-60秒。
  5. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述步骤S4中，恒温设备为鼓风干燥机、流化床、油浴锅或可通入蒸汽的反应釜，恒温设备的温度为100-200℃，恒温时间为5-60秒。
  6. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述步骤S1和S2中，预混均在分散机中进行，熔融共混均在挤出机中进行。
  7. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述共混粒子Ⅰ中，填料为核，改性剂为壳。
  8. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述步骤2中，得到的具有沙袋结构嵌段聚醚酰胺共混粒子单颗重量为4-50mg，长径比为5：1。
  9. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述步骤4中，得到的具有沙袋结构嵌段聚醚酰胺发泡粒子，密度为0.01-0.5g/cm3，单颗粒子重量在4-50mg，长径比为5：1。
  10. 根据权利要1所述的一种具有沙袋结构嵌段聚醚酰胺发泡粒子的制备方法，其特征在于：所述共混粒子Ⅲ中，发泡剂的含量为0.5％-20％。
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