CN113005536A - 一种新型纳米级塑料颗粒及其制备方法 - Google Patents
一种新型纳米级塑料颗粒及其制备方法 Download PDFInfo
- Publication number
- CN113005536A CN113005536A CN202110262833.5A CN202110262833A CN113005536A CN 113005536 A CN113005536 A CN 113005536A CN 202110262833 A CN202110262833 A CN 202110262833A CN 113005536 A CN113005536 A CN 113005536A
- Authority
- CN
- China
- Prior art keywords
- plastic
- plastic particles
- spinning
- organic solvent
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 67
- 229920003023 plastic Polymers 0.000 title claims abstract description 67
- 239000002245 particle Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000009987 spinning Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 16
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 16
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 7
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- KJOZJSGOIJQCGA-UHFFFAOYSA-N dichloromethane;2,2,2-trifluoroacetic acid Chemical group ClCCl.OC(=O)C(F)(F)F KJOZJSGOIJQCGA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001878 scanning electron micrograph Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000027 toxicology Toxicity 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000008092 positive effect Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 abstract 2
- 238000001523 electrospinning Methods 0.000 abstract 1
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000002110 toxicologic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
本发明公开了一种新型纳米级塑料颗粒及其制备方法。先将塑料粉末常温下溶解于有机溶剂中,得到均一稳定的纺丝液,用玻璃注射器吸取,固定到静电纺丝装置中,调节相应参数制备纳米级塑料颗粒。此方法适用于可溶于相应有机溶剂的塑料,有机溶剂优选体积比为9∶1的三氟乙酸二氯甲烷溶液,塑料优选聚对苯二甲酸乙二醇酯(PET);此方法得到的塑料颗粒粒径为纳米级,几乎不含珠丝状结构的纤维;不含表面活性剂等其他化学物质,通过超声处理也能得到分散性较强的微球悬浊液,用于毒理学实验可取得积极效果;制备时间相比于沉淀法较短;方法无需氮气保护加热系统,装置相比化学合成法简单。
Description
技术领域
本发明涉及环境材料领域,尤其涉及一种针对纳米塑料颗粒定量检测、毒理学分析所需材料的制备方法。
背景技术
塑料是现代生产生活中应用最广泛的材料之一,因环境作用破碎形成的微塑料和纳米塑料成为学者关注的新型污染物之一。相比于微塑料,纳米塑料具备更小的直径和更大的比表面积,也因此具有更强的生物渗透性和细胞吸附力,可能对生物造成远强于微塑料的毒性作用。为探究纳米塑料的生物毒性效应,研究者们最常使用纳米聚苯乙烯(PS)微球进行毒理学实验,但由于环境中塑料种类繁多,目前通用的实验材料过于单一,且所用的化学合成法所需的氮气保护合成条件较为复杂苛刻,通常得到的是含有表面活性剂等添加剂干扰的纳米塑料,获得更准确科学的纳米塑料毒理学研究数据支持十分必要。于晴利用静电纺丝技术制备PS微球解决了化学合成法实验条件严苛、含有添加剂干扰的问题,但其粒径分布在2-6μm的范围内,属于微米级的塑料颗粒,并含有大量珠丝状结构,这种纤维结构会极大影响塑料颗粒的毒理学实验结果。(于晴.2018.静电纺丝法制备聚苯乙烯复合膜的研究[硕士学位论文].李翀.哈尔滨工程大学.)高纯度的适用于毒理学研究的纳米级塑料颗粒制备尚未有相关报道。
本发明提出一种利用静电纺丝法制备高纯、几乎无珠丝状结构的纳米级塑料颗粒的方法,相比另一种常用的沉淀法耗时更短,是一种更具备通用性和实用性的纳米塑料颗粒制备手段。
发明内容
本发明提供了一种新型纳米级塑料颗粒及其制备方法。
先将塑料粉末常温下溶解于有机溶剂中,得到均一稳定的纺丝液,用玻璃注射器吸取,固定到静电纺丝装置中,调节相应参数制备纳米级塑料颗粒,具体步骤如下:
(1)将塑料粉末过200目筛,称取适量塑料粉末,在有机溶剂中室温搅拌24h使其完全溶解,形成稳定均匀的纺丝液;(2)将纺丝液注入玻璃注射器中静置以去除气泡,连接针头,利用注射器推进纺丝液至针头后,将注射器固定在注射泵槽口中;(3)将铝箔纸缠绕到金属制滚轮接收器上,调整转速后开启滚轮;(4)设定纺丝电压和推进速度,调节接收装置和推进装置之间的距离,开始纺丝制备微球;(5)纺丝完毕后,将铝箔纸置于50℃真空烘箱中干燥24h,通过扫描电镜得到SEM图像统计微球的粒径;
所述纳米级塑料颗粒的粒径为50-1000nm,几乎不含珠丝状结构;
所述有机溶剂为可溶解相应塑料的有机试剂,优选的,所述有机溶剂为体积比9∶1的三氟乙酸二氯甲烷溶液;
所述塑料为可溶于相应有机溶剂的塑料种类,优选地,所述塑料为聚对苯二甲酸乙二醇酯(PET);
所述纺丝液的浓度为质量分数0.25-0.5%;
所述接收装置金属制滚轮转速为100-110r/min;
所述纺丝电压为12-15kV;
所述推进速度为0.8-1.0mL/h;
所述接收装置和推进装置之间的距离为10-20cm。
本发明的积极效果如下:
此方法得到的塑料颗粒粒径为纳米级,几乎不含珠丝状结构的纤维;不含表面活性剂等其他化学物质,通过超声处理也能得到分散性较强的微球悬浊液,用于毒理学实验可取得积极效果;制备时间相比于沉淀法较短;方法无需氮气保护加热系统,装置相比化学合成法简单。
附图说明
图1为实例1制备的纳米PET塑料颗粒的SEM图像;
图2为实例2制备的纳米PET塑料颗粒的SEM图像;
图3为实例2制备的纳米PET塑料颗粒的红外谱图。
具体实施方式
下面的实例是对本发明的进一步详细描述:
实例1:
将PET塑料粉末过200目筛,称取0.75g置于100mL锥形瓶中,加入30mL体积比9∶1的三氟乙酸二氯甲烷溶液,室温搅拌24h使其完全溶解,形成质量分数0.25%的稳定均匀的纺丝液;将纺丝液注入5mL玻璃注射器中静置以去除气泡,连接直径1.25mm的毛细管针头,利用注射器推进纺丝液至针头后,将注射器固定在注射泵槽口中;接收装置上,将铝箔纸缠绕到金属制滚轮接收器上,并用胶带固定,接收器转速调至100r/min;设定纺丝电压为15kV,推进速度为0.8mL/h,调节接收装置和推进装置之间的距离为20cm,开启静电纺丝装置;纺丝完毕后,将铝箔纸置于50℃真空烘箱中干燥24h,通过扫描电镜得到SEM图像,利用Image-Pro软件统计微球的粒径,结果如图1所示,粒径为99.37-913.49nm,平均粒径为392.26nm,几乎不含珠丝状结构。
实例2:
将PET塑料粉末过200目筛,称取0.75g置于100mL锥形瓶中,加入30mL体积比9∶1的三氟乙酸二氯甲烷溶液,室温搅拌24h使其完全溶解,形成质量分数0.25%的稳定均匀的纺丝液;将纺丝液注入5mL玻璃注射器中静置以去除气泡,连接直径1.25mm的毛细管针头,利用注射器推进纺丝液至针头后,将注射器固定在注射泵槽口中;接收装置上,将铝箔纸缠绕到金属制滚轮接收器上,并用胶带固定,接收器转速调至100r/min;设定纺丝电压为15kV,推进速度为1.0mL/h,调节接收装置和推进装置之间的距离为15cm,开启静电纺丝装置;纺丝完毕后,将铝箔纸置于50℃真空烘箱中干燥24h,通过扫描电镜得到SEM图像,利用Image-Pro软件统计微球的粒径,结果如图2所示,粒径为111.11-959.68nm,平均粒径为328.16nm,几乎不含珠丝状结构;使用8700激光红外系统对塑料颗粒进行定性扫描,红外谱图如图3所示,验证其确实为PET塑料。
本发明公开一种新型纳米级塑料颗粒及其制备方法,本领域技术人员可通过借鉴本文内容,适当改变工艺路线等环节实现,尽管本发明的方法已通过较佳实施例进行了描述,相关技术人员明显能在不脱离本发明内容与范围内对本文所述方法进行改动或重新组合,实现最终结果。特别需要指出的是,所有相类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本发明的内容和范围中。
Claims (9)
1.一种新型纳米级塑料颗粒及其制备方法,其特征在于,先将塑料粉末常温下溶解于有机溶剂中,得到均一稳定的纺丝液,用玻璃注射器吸取,固定到静电纺丝装置中,调节相应参数制备纳米级塑料颗粒,具体步骤如下:
(1)将塑料粉末过200目筛,称取适量塑料粉末,在有机溶剂中室温搅拌24h使其完全溶解,形成稳定均匀的纺丝液;(2)将纺丝液注入玻璃注射器中静置以去除气泡,连接针头,利用注射器推进纺丝液至针头后,将注射器固定在注射泵槽口中;(3)将铝箔纸缠绕到金属制滚轮接收器上,调整转速后开启滚轮;(4)设定纺丝电压和推进速度,调节接收装置和推进装置之间的距离,开始纺丝制备微球;(5)纺丝完毕后,将铝箔纸置于50℃真空烘箱中干燥24h,通过扫描电镜得到SEM图像统计微球的粒径。
2.根据权利要求1所述一种新型纳米级塑料颗粒,其特征在于:纳米级塑料颗粒的粒径为50-1000nm,几乎不含珠丝状结构。
3.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于,所述有机溶剂为可溶解相应塑料的有机试剂,优选的,所述有机溶剂为体积比9∶1的三氟乙酸二氯甲烷溶液。
4.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于,所述塑料为可溶于相应有机溶剂的塑料种类,优选地,所述塑料为聚对苯二甲酸乙二醇酯(PET)。
5.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于:纺丝液的浓度为质量分数0.25-0.5%。
6.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于:接收装置金属制滚轮转速为100-110r/min。
7.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于:纺丝电压为12-15kV。
8.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于:推进速度为0.8-1.0mL/h。
9.根据权利要求1所述一种新型纳米级塑料颗粒的制备方法,其特征在于:接收装置和推进装置之间的距离为10-20cm。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110262833.5A CN113005536A (zh) | 2021-03-11 | 2021-03-11 | 一种新型纳米级塑料颗粒及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110262833.5A CN113005536A (zh) | 2021-03-11 | 2021-03-11 | 一种新型纳米级塑料颗粒及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113005536A true CN113005536A (zh) | 2021-06-22 |
Family
ID=76404688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110262833.5A Pending CN113005536A (zh) | 2021-03-11 | 2021-03-11 | 一种新型纳米级塑料颗粒及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113005536A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116121844A (zh) * | 2023-04-04 | 2023-05-16 | 南通海星电子股份有限公司 | 一种铝箔发孔阶段所用复合电极的制备方法 |
WO2024005698A1 (en) | 2022-06-30 | 2024-01-04 | Cellucircle Ab | A method for melt processing of textile waste material and products obtained by the method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102160191A (zh) * | 2008-08-29 | 2011-08-17 | 索尔维公司 | 含电纺丝法生产的聚合物纳米纤维的电解质以及使用它的高效率染料敏化太阳能电池 |
CN102787390A (zh) * | 2012-08-16 | 2012-11-21 | 东华大学 | 高压静电喷雾制备pei/pmma复合纳米微球的方法 |
WO2015027880A1 (en) * | 2013-08-26 | 2015-03-05 | Institute Of Chemistry, Chinese Academy Of Sciences | Photonic crystal microsphere |
CN108078954A (zh) * | 2017-12-14 | 2018-05-29 | 吉林大学 | 一种利用静电纺丝机同轴制备可注射plga载药微球的方法 |
-
2021
- 2021-03-11 CN CN202110262833.5A patent/CN113005536A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102160191A (zh) * | 2008-08-29 | 2011-08-17 | 索尔维公司 | 含电纺丝法生产的聚合物纳米纤维的电解质以及使用它的高效率染料敏化太阳能电池 |
CN102787390A (zh) * | 2012-08-16 | 2012-11-21 | 东华大学 | 高压静电喷雾制备pei/pmma复合纳米微球的方法 |
WO2015027880A1 (en) * | 2013-08-26 | 2015-03-05 | Institute Of Chemistry, Chinese Academy Of Sciences | Photonic crystal microsphere |
CN108078954A (zh) * | 2017-12-14 | 2018-05-29 | 吉林大学 | 一种利用静电纺丝机同轴制备可注射plga载药微球的方法 |
Non-Patent Citations (2)
Title |
---|
于晴: "《静电纺丝法制备聚苯乙烯复合膜的研究》", 《中国优秀硕士学位论文全文数据库》 * |
刘颖琦: "《静电纺丝 PET 膜结晶性能研究》", 《山东化工》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024005698A1 (en) | 2022-06-30 | 2024-01-04 | Cellucircle Ab | A method for melt processing of textile waste material and products obtained by the method |
CN116121844A (zh) * | 2023-04-04 | 2023-05-16 | 南通海星电子股份有限公司 | 一种铝箔发孔阶段所用复合电极的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Moheman et al. | Recent trends in electrospinning of polymer nanofibers and their applications in ultra thin layer chromatography | |
Hu et al. | One‐step electro‐spinning/netting technique for controllably preparing polyurethane nano‐fiber/net | |
CN100572619C (zh) | 一种制备规则排列高分子纳米纤维的装置和方法 | |
Li et al. | Multifunctional and efficient air filtration: a natural nanofilter prepared with zein and polyvinyl alcohol | |
Sawicka et al. | Metal oxide nanowires for use in chemical sensing applications | |
Roso et al. | Multifunctional membranes based on spinning technologies: the synergy of nanofibers andnanoparticles | |
Guo et al. | Electrospinning polyethylene terephthalate/SiO2 nanofiber composite needle felt for enhanced filtration performance | |
Zhang et al. | Spraying functional fibres by electrospinning | |
CN113005536A (zh) | 一种新型纳米级塑料颗粒及其制备方法 | |
Li et al. | Coaxial electrospinning and characterization of core-shell structured cellulose nanocrystal reinforced PMMA/PAN composite fibers | |
Yuan et al. | Structural evolution of electrospun composite fibers from the blend of polyvinyl alcohol and polymer nanoparticles | |
CN103103629B (zh) | 一种富勒烯-高分子复合纳米纤维及其制备方法 | |
Wang et al. | Electrospun poly (methyl methacrylate) nanofibers and microparticles | |
Korotcenkov | Electrospun metal oxide nanofibers and their conductometric gas sensor application. Part 1: Nanofibers and features of their forming | |
CN112981725A (zh) | 纳米纤维膜、温敏性Janus复合膜及其制备方法 | |
Xie et al. | Highly stable coated polyvinylpyrrolidone nanofibers prepared using modified coaxial electrospinning | |
Sun et al. | Self‐Assembly and Metallization of Resorcinarene Microtubes in Water | |
CN102794140A (zh) | 粒径可控的核壳Fe3O4/SiO2纳米粒的制备方法 | |
Yan et al. | Smoothening electrospinning and obtaining high-quality cellulose acetate nanofibers using a modified coaxial process | |
CN104562436A (zh) | 一种表面结构可控的纤维膜及其制备方法 | |
Chang et al. | Submicron PAN and nanofiber CTA air filters: Fabrication, optimization, and performance | |
CN108654528A (zh) | 磁性高分子核壳结构微球及其制备方法和应用 | |
CN102697727B (zh) | 一种利用静电纺丝技术制备自组装酮洛芬脂质体的方法 | |
CN103011178A (zh) | 一种球形SiO2颗粒的制备方法 | |
CN106189375A (zh) | 一种活性碳纳米管 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210622 |
|
WD01 | Invention patent application deemed withdrawn after publication |