CN114673003A - 一种高耐刮纤维薄膜及其制备方法 - Google Patents
一种高耐刮纤维薄膜及其制备方法 Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
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- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000001816 cooling Methods 0.000 claims description 17
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920006255 plastic film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种高耐刮纤维薄膜及其制备方法,涉及纤维薄膜技术领域。本发明在制备高耐刮纤维薄膜时,先将碳纳米纤维和浓硫酸混合并依次和高锰酸钾、过氧化氢、一氯乙酸反应制得预改性碳纳米纤维,将聚乙二醇和3‑[3‑羧基烯丙酰胺基]丙基三乙氧基硅烷反应后再和预改性碳纳米纤维反应制得改性碳纳米纤维,将改性碳纳米纤维、钛酸四丁酯和正硅酸乙酯反应制得沉积膜,将聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜混合并进行密封搅拌制得纳米纤维溶液,以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理后制得高耐刮纤维薄膜。本发明制备的高耐刮纤维薄膜具有优良的耐刮擦性能和抗静电性能。
Description
技术领域
本发明涉及纤维薄膜技术领域,具体为一种高耐刮纤维薄膜及其制备方法。
背景技术
薄膜是一种薄而软的透明薄片。用塑料、胶粘剂、橡胶或其他材料制成。薄膜科学上的解释为:由原子,分子或离子沉积在基片表面形成的2维材料。例:光学薄膜、复合薄膜、超导薄膜、聚酯薄膜、尼龙薄膜、塑料薄膜等等。薄膜被广泛用于电子电器,机械,印刷等行业。
随着科技的发展,薄膜在日常生活用品上的应用随处可见,如电子屏幕上的保护膜和防蓝光薄膜,车用的防晒薄膜,私人场所用的防窥薄膜等,在薄膜材料具有各种各样的性能的同时,人们对于薄膜的防护性要求也越来越高,由于薄膜的厚度较小,不能起到有效的防护效果,常用纤维或其他填充物来增强薄膜的防护性,但达到的效果较为有限,本发明制得的纤维薄膜具有良好的耐刮擦性。
发明内容
本发明的目的在于提供一种高耐刮纤维薄膜及其制备方法,以解决现有技术中存在的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种高耐刮纤维薄膜的制备方法,其特征在于,所述高耐刮纤维薄膜是将改性碳纳米纤维、钛酸四丁酯和正硅酸乙酯反应制得沉积膜,以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理后制得。
作为优化,所述改性碳纳米纤维是将碳纳米纤维和浓硫酸混合并依次和高锰酸钾、过氧化氢、一氯乙酸反应制得预改性碳纳米纤维,将聚乙二醇和3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷反应后再和预改性碳纳米纤维反应制得。
作为优化,所述纳米纤维溶液是将聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜混合并进行密封搅拌制得。
作为优化,所述高耐刮纤维薄膜的制备方法包括以下制备步骤:
(1)将聚乙二醇、质量分数90~98%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2:8:1~3:10:1混合均匀,在氮气氛围中,90~100℃,500~800r/min搅拌反应60~80min,在1~2kPa静置30~40min,再加入聚乙二醇质量3~5倍的的预改性碳纳米纤维继续搅拌反应60~80min,在1~2kPa静置30~40min,冷却至室温加入碳酸氢钠将pH调节至6.8~7.2,过滤并用乙醇洗涤3~5次,制得改性碳纳米纤维;
(2)将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比10:8:5:1:30~15:10:7:1:40混合均匀,在20~30℃,1500~2000r/min搅拌下以0.3~0.5mL/s的速度滴加改性碳纳米纤维质量4~6倍的氨水乙醇溶液,滴加后继续以相同转速搅拌3~5min,在30~40kHz超声10~15min,静置3~5h,将沉积物取出,在纯水中浸洗3~5min,在-1~-10℃,5~10Pa干燥6~8h,制得沉积膜;
(3)以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理,再取出并置于二甲基亚砜中在30~40kHz超声10~15min,在-1~-10℃,5~10Pa干燥6~8h,制得高耐刮纤维薄膜。
作为优化,步骤(1)所述聚乙二醇的分子量为400~500。
作为优化,步骤(1)所述改性碳纳米纤维的制备方法为:将碳纳米纤维与质量分数为90~98%的浓硫酸按质量比1:6~1:8混合均匀,加入碳纳米纤维质量0.8~1.2倍的高锰酸钾,在50~60℃,30~40kHz超声反应4~6h,再降温至1~5℃并加入碳纳米纤维质量0.1~0.3倍的过氧化氢,以800~1000r/min搅拌反应10~15min后,过滤并用纯水洗涤3~5次,再与碳纳米纤维质量100~120倍的纯水混合均匀,再加入碳纳米纤维质量20~30倍的氢氧化钠和碳纳米纤维质量15~25倍的一氯乙酸,在50~60℃,30~40kHz超声反应3~4h,并在60~70℃过滤,用质量分数1~3%的盐酸溶液和纯水各洗涤3~5次,在-10~-5℃温度,5~10Pa压力下干燥4~6h,制备而成。
作为优化,步骤(2)所述氨水乙醇溶液是将质量分数15~20%的氨水和无水乙醇按质量比1:5~1:6混合均匀配制而成。
作为优化,步骤(2)所述纳米纤维溶液是将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比4:1:5:200~6:1:5:300混合均匀,在密封环境中,20~30℃,1000~1500r/min搅拌100~150h,配置而成。
作为优化,所述剪切后的聚对苯二甲酰胺对苯二胺纤维线是将聚对苯二甲酰胺对苯二胺纤维线剪切成2~3cm长度制得。
作为优化,步骤(3)所述真空抽滤处理的方法为:将纳米纤维溶液以每次沉积膜质量20~30倍的量进行5~6次真空抽滤,每次真空抽滤后再加入纯水和无水乙醇各抽滤3~5min。
与现有技术相比,本发明所达到的有益效果是:
本发明在制备高耐刮纤维薄膜时,将改性碳纳米纤维、钛酸四丁酯和正硅酸乙酯反应制得沉积膜,将聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜混合并进行密封搅拌制得纳米纤维溶液,以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理后制得高耐刮纤维薄膜。
首先,将碳纳米纤维和浓硫酸混合并依次和高锰酸钾、过氧化氢、一氯乙酸反应制得预改性碳纳米纤维,将聚乙二醇和3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷反应后再和预改性碳纳米纤维反应制得改性碳纳米纤维,一氯乙酸可以将碳纳米纤维在反应过程中产生的环氧基和羟基转化为羧基,避免在后一步浓硫酸中反应时产生自身的脱水反应而交联团聚,进一步导致在最终成型的高耐刮纤维薄膜中碳纳米纤维分布不均并使形成的碳纳米纤维导电通路效果降低,从而高耐刮纤维薄膜的抗静电性能;真空抽滤处理,在抽滤过程中能持续不断的清楚小分子和金属离子,碱性环境使聚乙二醇和主体的酯键水解,聚乙二醇溢出,为纳米纤维溶液提供结合空位,纳米纤维溶液中的聚对苯二甲酰胺对苯二胺的酰胺键位置上的氢被氢氧化钠吸附从而带正电,改性碳纳米纤维产生的羧酸基团正负电结合,从而高耐刮纤维薄膜的抗静电性能。
其次,钛酸四丁酯和正硅酸乙酯水解聚合生产的纳米二氧化硅和纳米二氧化钛复合粒子,复合粒子与改性碳纳米纤维上的三乙氧基硅基团水解产生的硅羟基结合,使复合粒子均匀分布在整体形成受力节点,从而高耐刮纤维薄膜的耐刮擦性能,同时由于复合粒子表面具有大量的羟基,在抽滤时氢氧化钠中产生氧离子空位并捕获氢氧化钠的钠离子,催化改性碳纳米纤维上的羰基发生羟醛缩合反应,增加了改性碳纳米纤维之间的交联程度,从而高耐刮纤维薄膜的耐刮擦性能,提高了改性碳纳米纤维的溶解性。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为了更清楚的说明本发明提供的方法通过以下实施例进行详细说明,在以下实施例中制作的高耐刮纤维薄膜的各指标测试方法如下:
耐刮擦性能:将各实施例所得的高耐刮纤维薄膜与对比例材料取相同大小形状面积厚度,与固定在玻璃载体上用刮擦测试仪在相同参数下进行刮擦试验,对挂擦试验后的材料清洗表面后称重,记录损失质量。
抗静电性:将各实施例所得的高耐刮纤维薄膜与对比例材料取相同大小形状面积厚度,按照GB/T15662标准法测定体积电阻率来测定抗静电性。
实施例1
一种高耐刮纤维薄膜的制备方法,所述高耐刮纤维薄膜的制备方法主要包括以下制备步骤:
(1)将碳纳米纤维与质量分数为98%的浓硫酸按质量比1:6混合均匀,加入碳纳米纤维质量0.8倍的高锰酸钾,在50℃,30kHz超声反应6h,再降温至1℃并加入碳纳米纤维质量0.1倍的过氧化氢,以800r/min搅拌反应15min后,过滤并用纯水洗涤3次,再与碳纳米纤维质量100倍的纯水混合均匀,再加入碳纳米纤维质量20倍的氢氧化钠和碳纳米纤维质量15倍的一氯乙酸,在50℃,30kHz超声反应4h,并在60℃过滤,用质量分数1%的盐酸溶液和纯水各洗涤3次,在-10℃温度,5Pa压力下干燥6h,制得预改性碳纳米纤维,将分子量400的聚乙二醇、质量分数90%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2:8:1混合均匀,在氮气氛围中,90℃,500r/min搅拌反应60min,在1kPa静置30min,再加入聚乙二醇质量3倍的的预改性碳纳米纤维继续搅拌反应80min,在1kPa静置40min,冷却至室温加入碳酸氢钠将pH调节至6.8,过滤并用乙醇洗涤3次,在-1℃,5Pa干燥6h,制得改性碳纳米纤维;
(2)将质量分数20%的氨水和无水乙醇按质量比1:5混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比10:8:5:1:30混合均匀,在20℃,1500r/min搅拌下以0.3mL/s的速度滴加改性碳纳米纤维质量4倍的氨水乙醇溶液,滴加后继续以相同转速搅拌4min,在30kHz超声15min,静置5h,将沉积物取出,在纯水中浸洗3min,在-1℃,5Pa干燥6h,制得沉积膜;
(3)将聚对苯二甲酰胺对苯二胺纤维线剪切成2cm长度,将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比4:1:5:200混合均匀,在密封环境中,20℃,1000r/min搅拌120h,制得纳米纤维溶液;以沉积膜为滤膜,将纳米纤维溶液以每次沉积膜质量20倍的量进行6次真空抽滤,每次真空抽滤后再加入纯水和无水乙醇各抽滤5min,取出后置于二甲基亚砜中在30kHz超声15min,在-1℃,5Pa干燥8h,制得高耐刮纤维薄膜。
实施例2
一种高耐刮纤维薄膜的制备方法,所述高耐刮纤维薄膜的制备方法主要包括以下制备步骤:
(1)将碳纳米纤维与质量分数为94%的浓硫酸按质量比1:7混合均匀,加入碳纳米纤维质量1倍的高锰酸钾,在55℃,35kHz超声反应5h,再降温至3℃并加入碳纳米纤维质量0.2倍的过氧化氢,以900r/min搅拌反应12min后,过滤并用纯水洗涤4次,再与碳纳米纤维质量110倍的纯水混合均匀,再加入碳纳米纤维质量25倍的氢氧化钠和碳纳米纤维质量20倍的一氯乙酸,在55℃,35kHz超声反应3.5h,并在65℃过滤,用质量分数2%的盐酸溶液和纯水各洗涤4次,在-8℃温度,8Pa压力下干燥5h,制得预改性碳纳米纤维,将分子量450的聚乙二醇、质量分数94%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2.5:9:1混合均匀,在氮气氛围中,95℃,650r/min搅拌反应70min,在1.5kPa静置35min,再加入聚乙二醇质量4倍的的预改性碳纳米纤维继续搅拌反应70min,在1.5kPa静置35min,冷却至室温加入碳酸氢钠将pH调节至7,过滤并用乙醇洗涤4次,在-5℃,8Pa干燥7h,制得改性碳纳米纤维;
(2)将质量分数18%的氨水和无水乙醇按质量比1:5.5混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比13:9:6:1:35混合均匀,在25℃,1800r/min搅拌下以0.4mL/s的速度滴加改性碳纳米纤维质量5倍的氨水乙醇溶液,滴加后继续以相同转速搅拌4min,在35kHz超声12min,静置4h,将沉积物取出,在纯水中浸洗4min,在-5℃,8Pa干燥7h,制得沉积膜;
(3)将聚对苯二甲酰胺对苯二胺纤维线剪切成2.5cm长度,将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比5:1:5:250混合均匀,在密封环境中,25℃,1200r/min搅拌120h,制得纳米纤维溶液;以沉积膜为滤膜,将纳米纤维溶液以每次沉积膜质量25倍的量进行5次真空抽滤,每次真空抽滤后再加入纯水和无水乙醇各抽滤4min,取出后置于二甲基亚砜中在35kHz超声12min,在-5℃,8Pa干燥7h,制得高耐刮纤维薄膜。
实施例3
一种高耐刮纤维薄膜的制备方法,所述高耐刮纤维薄膜的制备方法主要包括以下制备步骤:
(1)将碳纳米纤维与质量分数为90%的浓硫酸按质量比1:8混合均匀,加入碳纳米纤维质量1.2倍的高锰酸钾,在60℃,40kHz超声反应4h,再降温至5℃并加入碳纳米纤维质量0.3倍的过氧化氢,以1000r/min搅拌反应10min后,过滤并用纯水洗涤5次,再与碳纳米纤维质量120倍的纯水混合均匀,再加入碳纳米纤维质量30倍的氢氧化钠和碳纳米纤维质量25倍的一氯乙酸,在60℃,40kHz超声反应3h,并在70℃过滤,用质量分数3%的盐酸溶液和纯水各洗涤5次,在-5℃温度,10Pa压力下干燥4h,制得预改性碳纳米纤维,将分子量500的聚乙二醇、质量分数90%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比3:10:1混合均匀,在氮气氛围中,100℃,800r/min搅拌反应60min,在2kPa静置40min,再加入聚乙二醇质量5倍的的预改性碳纳米纤维继续搅拌反应60min,在2kPa静置40min,冷却至室温加入碳酸氢钠将pH调节至7.2,过滤并用乙醇洗涤5次,在-10℃,10Pa干燥6h,制得改性碳纳米纤维;
(2)将质量分数20%的氨水和无水乙醇按质量比1:6混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比15:10:7:1:40混合均匀,在30℃,2000r/min搅拌下以0.3mL/s的速度滴加改性碳纳米纤维质量6倍的氨水乙醇溶液,滴加后继续以相同转速搅拌5min,在40kHz超声10min,静置5h,将沉积物取出,在纯水中浸洗5min,在-10℃,10Pa干燥6h,制得沉积膜;
(3)将聚对苯二甲酰胺对苯二胺纤维线剪切成3cm长度,将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比6:1:5:300混合均匀,在密封环境中,30℃,1500r/min搅拌100h,制得纳米纤维溶液;以沉积膜为滤膜,将纳米纤维溶液以每次沉积膜质量30倍的量进行5次真空抽滤,每次真空抽滤后再加入纯水和无水乙醇各抽滤5min,取出后置于二甲基亚砜中在40kHz超声10min,在-10℃,10Pa干燥6h,制得高耐刮纤维薄膜。
对比例1
对比例1的高耐刮纤维薄膜的制备方法与实施例2的区别仅在于步骤(1)的不同,将步骤(1)修改为:将碳纳米纤维与质量分数为94%的浓硫酸按质量比1:7混合均匀,加入碳纳米纤维质量1倍的高锰酸钾,在55℃,35kHz超声反应5h,再降温至3℃并加入碳纳米纤维质量0.2倍的过氧化氢,以900r/min搅拌反应12min后,过滤并用纯水洗涤4次,在-8℃温度,8Pa压力下干燥5h,制得预改性碳纳米纤维,将分子量450的聚乙二醇、质量分数94%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2.5:9:1混合均匀,在氮气氛围中,95℃,650r/min搅拌反应70min,在1.5kPa静置35min,再加入聚乙二醇质量4倍的的预改性碳纳米纤维继续搅拌反应70min,在1.5kPa静置35min,冷却至室温加入碳酸氢钠将pH调节至7,过滤并用乙醇洗涤4次,在-5℃,8Pa干燥7h,制得改性碳纳米纤维。其余步骤同时实施例2。
对比例2
对比例2的高耐刮纤维薄膜的制备方法与实施例2的区别仅在于步骤(1)的不同,将步骤(1)修改为:将碳纳米纤维与质量分数为94%的浓硫酸按质量比1:7混合均匀,加入碳纳米纤维质量1倍的高锰酸钾,在55℃,35kHz超声反应5h,再降温至3℃并加入碳纳米纤维质量0.2倍的过氧化氢,以900r/min搅拌反应12min后,过滤并用纯水洗涤4次,在-8℃温度,8Pa压力下干燥5h,制得改性碳纳米纤维。其余步骤同时实施例2。
对比例3
对比例3的高耐刮纤维薄膜的制备方法与实施例2的区别仅在于步骤(2)的不同,将步骤(2)修改为:将质量分数18%的氨水和无水乙醇按质量比1:5.5混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比13:15:1:35混合均匀,在25℃,1800r/min搅拌下以0.4mL/s的速度滴加改性碳纳米纤维质量5倍的氨水乙醇溶液,滴加后继续以相同转速搅拌4min,在35kHz超声12min,静置4h,将沉积物取出,在纯水中浸洗4min,在-5℃,8Pa干燥7h,制得沉积膜。其余步骤同时实施例2。
对比例4
一种高耐刮纤维薄膜的制备方法,所述高耐刮纤维薄膜的制备方法主要包括以下制备步骤:
(1)将碳纳米纤维与质量分数为94%的浓硫酸按质量比1:7混合均匀,加入碳纳米纤维质量1倍的高锰酸钾,在55℃,35kHz超声反应5h,再降温至3℃并加入碳纳米纤维质量0.2倍的过氧化氢,以900r/min搅拌反应12min后,过滤并用纯水洗涤4次,再与碳纳米纤维质量110倍的纯水混合均匀,再加入碳纳米纤维质量25倍的氢氧化钠和碳纳米纤维质量20倍的一氯乙酸,在55℃,35kHz超声反应3.5h,并在65℃过滤,用质量分数2%的盐酸溶液和纯水各洗涤4次,在-8℃温度,8Pa压力下干燥5h,制得预改性碳纳米纤维,将分子量450的聚乙二醇、质量分数94%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2.5:9:1混合均匀,在氮气氛围中,95℃,650r/min搅拌反应70min,在1.5kPa静置35min,再加入聚乙二醇质量4倍的的预改性碳纳米纤维继续搅拌反应70min,在1.5kPa静置35min,冷却至室温加入碳酸氢钠将pH调节至7,过滤并用乙醇洗涤4次,在-5℃,8Pa干燥7h,制得改性碳纳米纤维;
(2)将聚对苯二甲酰胺对苯二胺纤维线剪切成2.5cm长度,将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比5:1:5:250混合均匀,在密封环境中,25℃,1200r/min搅拌120h,制得纳米纤维溶液;将质量分数18%的氨水和无水乙醇按质量比1:5.5混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比13:9:6:1:35混合均匀,在25℃,1800r/min搅拌下以0.4mL/s的速度滴加改性碳纳米纤维质量5倍的氨水乙醇溶液,滴加后继续以相同转速搅拌4min,再加入改性碳纳米纤维质量180倍的纳米纤维溶液,在35kHz超声12min,静置4h,将沉积物取出,在纯水中浸洗4min,在二甲基亚砜中在35kHz超声12min,在-5℃,8Pa干燥7h,制得高耐刮纤维薄膜。
对比例5
一种高耐刮纤维薄膜的制备方法,所述高耐刮纤维薄膜的制备方法主要包括以下制备步骤:
(1)将碳纳米纤维与质量分数为94%的浓硫酸按质量比1:7混合均匀,加入碳纳米纤维质量1倍的高锰酸钾,在55℃,35kHz超声反应5h,再降温至3℃并加入碳纳米纤维质量0.2倍的过氧化氢,以900r/min搅拌反应12min后,过滤并用纯水洗涤4次,再与碳纳米纤维质量110倍的纯水混合均匀,再加入碳纳米纤维质量25倍的氢氧化钠和碳纳米纤维质量20倍的一氯乙酸,在55℃,35kHz超声反应3.5h,并在65℃过滤,用质量分数2%的盐酸溶液和纯水各洗涤4次,在-8℃温度,8Pa压力下干燥5h,制得预改性碳纳米纤维,将分子量450的聚乙二醇、质量分数94%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2.5:9:1混合均匀,在氮气氛围中,95℃,650r/min搅拌反应70min,在1.5kPa静置35min,再加入聚乙二醇质量4倍的的预改性碳纳米纤维继续搅拌反应70min,在1.5kPa静置35min,冷却至室温加入碳酸氢钠将pH调节至7,过滤并用乙醇洗涤4次,在-5℃,8Pa干燥7h,制得改性碳纳米纤维;
(2)将聚对苯二甲酰胺对苯二胺纤维线剪切成2.5cm长度,将剪切后的聚对苯二甲酰胺对苯二胺纤维线、纯水和二甲基亚砜按质量比5:5:250混合均匀,在密封环境中,25℃,1200r/min搅拌120h,制得纳米纤维溶液;将质量分数18%的氨水和无水乙醇按质量比1:5.5混合均匀配制成氨水乙醇溶液,将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比13:9:6:1:35混合均匀,在25℃,1800r/min搅拌下以0.4mL/s的速度滴加改性碳纳米纤维质量5倍的氨水乙醇溶液,滴加后继续以相同转速搅拌4min,再加入改性碳纳米纤维质量180倍的纳米纤维溶液,在35kHz超声12min,静置4h,将沉积物取出,在纯水中浸洗4min,在二甲基亚砜中在35kHz超声12min,在-5℃,8Pa干燥7h,制得高耐刮纤维薄膜。
效果例
下表1给出了采用本发明实施例1~3与对比例1~5的高耐刮纤维薄膜的耐刮擦性能和抗静电性能的性能分析结果。
表1
损失质量 | 体积电阻率 | 损失质量 | 体积电阻率 | ||
实施例1 | 0.03g | 171Ω*m | 对比例2 | 0.37g | 534Ω*m |
实施例2 | 0.02g | 152Ω*m | 对比例3 | 0.25g | 183Ω*m |
实施例3 | 0.03g | 157Ω*m | 对比例4 | 0.62g | 1652Ω*m |
对比例1 | 0.06g | 982Ω*m | 对比例5 | 0.72g | 3758Ω*m |
从表1中实施例1~3和对比例1~5的实验数据比较可发现,本发明制得的高耐刮纤维薄膜具有良好的耐刮擦性能和抗静电性能。
从实施例1、2、3和对比例1的实验数据比较可发现,实施例1、2、3对比对比例1的体积电阻率低,说明了在碳纳米纤维改性过程中加入一氯乙酸进行反应,一氯乙酸可以将碳纳米纤维在反应过程中产生的环氧基和羟基转化为羧基,避免在后一步浓硫酸中反应时产生自身的脱水反应而交联团聚,进一步导致在最终成型的高耐刮纤维薄膜中碳纳米纤维分布不均并使形成的碳纳米纤维导电通路效果降低,从而高耐刮纤维薄膜的抗静电性能;从实施例1、2、3和对比列2的实验数据比较可发现,实施例1、2、3对比对比例2的损失质量和体积电阻率低,说明了聚乙二醇和3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷反应后和预改性碳纳米纤维反应制得改性碳纳米纤维,提高了改性碳纳米纤维的溶解性,同时使三乙氧基硅烷基团在改性碳纳米纤维上分布,水解成硅羟基并连接钛酸四丁酯和正硅酸乙酯水解聚合生产的纳米二氧化硅和纳米二氧化钛复合粒子,使复合粒子均匀分布在整体形成受力节点,从而高耐刮纤维薄膜的耐刮擦性能,在对纳米纤维溶液进行抽滤时,碱性环境使聚乙二醇和主体的酯键水解,聚乙二醇溢出,为纳米纤维溶液提供结合空位,纳米纤维溶液中的聚对苯二甲酰胺对苯二胺的酰胺键位置上的氢被氢氧化钠吸附从而带正电,改性碳纳米纤维产生的羧酸基团正负电结合,从而高耐刮纤维薄膜的抗静电性能;从实施例1、2、3对比对比例3实验数据比较可发现,实施例1、2、3对比对比例3的损失质量低,说明了加入钛酸四丁酯,钛酸四丁酯和正硅酸乙酯水解聚合生产的纳米二氧化硅和纳米二氧化钛复合粒子,复合粒子表面具有大量的羟基,在氢氧化钠中产生氧离子空位并捕获氢氧化钠的钠离子,催化改性碳纳米纤维上的羰基发生羟醛缩合反应,增加了改性碳纳米纤维之间的交联程度,从而高耐刮纤维薄膜的耐刮擦性能;从实施例1、2、3对比对比例4、5实验数据比较可发现,实施例1、2、3对比对比例4、5的损失质量和体积电阻率低,说明了通过真空抽滤相较于直接混合沉积而言,在抽滤过程中能持续不断的清除小分子和金属离子,避免了持续的碱性环境对部分结构的破坏,无碱性环境聚对苯二甲酰胺对苯二胺的不溶,沉积膜中小分子的夹杂等问题,从而高耐刮纤维薄膜的耐刮擦性能和抗静电性能。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何标记视为限制所涉及的权利要求。
Claims (10)
1.一种高耐刮纤维薄膜的制备方法,其特征在于,所述高耐刮纤维薄膜是将改性碳纳米纤维、钛酸四丁酯和正硅酸乙酯反应制得沉积膜,以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理后制得。
2.根据权利要求1所述的一种高耐刮纤维薄膜的制备方法,其特征在于,所述改性碳纳米纤维是将碳纳米纤维和浓硫酸混合并依次和高锰酸钾、过氧化氢、一氯乙酸反应制得预改性碳纳米纤维,将聚乙二醇和3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷反应后再和预改性碳纳米纤维反应制得。
3.根据权利要求1所述的一种高耐刮纤维薄膜的制备方法,其特征在于,所述纳米纤维溶液是将聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜混合并进行密封搅拌制得。
4.根据权利要求1所述的一种高耐刮纤维薄膜的制备方法,其特征在于,所述高耐刮纤维薄膜的制备方法包括以下制备步骤:
(1)将聚乙二醇、质量分数90~98%的浓硫酸、3-[3-羧基烯丙酰胺基]丙基三乙氧基硅烷按质量比2:8:1~3:10:1混合均匀,在氮气氛围中,90~100℃,500~800r/min搅拌反应60~80min,在1~2kPa静置30~40min,再加入聚乙二醇质量3~5倍的的预改性碳纳米纤维继续搅拌反应60~80min,在1~2kPa静置30~40min,冷却至室温加入碳酸氢钠将pH调节至6.8~7.2,过滤并用乙醇洗涤3~5次,制得改性碳纳米纤维;
(2)将改性碳纳米纤维、钛酸四丁酯、正硅酸乙酯、乙酰丙酮和无水乙醇按质量比10:8:5:1:30~15:10:7:1:40混合均匀,在20~30℃,1500~2000r/min搅拌下以0.3~0.5mL/s的速度滴加改性碳纳米纤维质量4~6倍的氨水乙醇溶液,滴加后继续以相同转速搅拌3~5min,在30~40kHz超声10~15min,静置3~5h,将沉积物取出,在纯水中浸洗3~5min,在-1~-10℃,5~10Pa干燥6~8h,制得沉积膜;
(3)以沉积膜为滤膜,对纳米纤维溶液进行真空抽滤处理,再取出并置于二甲基亚砜中在30~40kHz超声10~15min,在-1~-10℃,5~10Pa干燥6~8h,制得高耐刮纤维薄膜。
5.根据权利要求4所述的一种高耐刮纤维薄膜的制备方法,其特征在于,步骤(1)所述聚乙二醇的分子量为400~500。
6.根据权利要求4所述的一种高耐刮纤维薄膜的制备方法,其特征在于,步骤(1)所述改性碳纳米纤维的制备方法为:将碳纳米纤维与质量分数为90~98%的浓硫酸按质量比1:6~1:8混合均匀,加入碳纳米纤维质量0.8~1.2倍的高锰酸钾,在50~60℃,30~40kHz超声反应4~6h,再降温至1~5℃并加入碳纳米纤维质量0.1~0.3倍的过氧化氢,以800~1000r/min搅拌反应10~15min后,过滤并用纯水洗涤3~5次,再与碳纳米纤维质量100~120倍的纯水混合均匀,再加入碳纳米纤维质量20~30倍的氢氧化钠和碳纳米纤维质量15~25倍的一氯乙酸,在50~60℃,30~40kHz超声反应3~4h,并在60~70℃过滤,用质量分数1~3%的盐酸溶液和纯水各洗涤3~5次,在-10~-5℃温度,5~10Pa压力下干燥4~6h,制备而成。
7.根据权利要求4所述的一种高耐刮纤维薄膜的制备方法,其特征在于,步骤(2)所述氨水乙醇溶液是将质量分数15~20%的氨水和无水乙醇按质量比1:5~1:6混合均匀配制而成。
8.根据权利要求4所述的一种高耐刮纤维薄膜的制备方法,其特征在于,步骤(2)所述纳米纤维溶液是将剪切后的聚对苯二甲酰胺对苯二胺纤维线、氢氧化钠固体、纯水和二甲基亚砜按质量比4:1:5:200~6:1:5:300混合均匀,在密封环境中,20~30℃,1000~1500r/min搅拌100~150h,配置而成。
9.根据权利要求8所述的一种高耐刮纤维薄膜的制备方法,其特征在于,所述剪切后的聚对苯二甲酰胺对苯二胺纤维线是将聚对苯二甲酰胺对苯二胺纤维线剪切成2~3cm长度制得。
10.根据权利要求4所述的一种高耐刮纤维薄膜的制备方法,其特征在于,步骤(3)所述真空抽滤处理的方法为:将纳米纤维溶液以每次沉积膜质量20~30倍的量进行5~6次真空抽滤,每次真空抽滤后再加入纯水和无水乙醇各抽滤3~5min。
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