CN110835846B - 一种维持线性聚苯乙烯材料原始形貌的交联改性方法 - Google Patents
一种维持线性聚苯乙烯材料原始形貌的交联改性方法 Download PDFInfo
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Abstract
本发明属于线性聚苯乙烯改性技术领域,具体公开一种维持线性聚苯乙烯材料原始形貌的交联改性方法。步骤如下:(1)、混合溶液的配制:在室温下,将正己烷、二乙氧基甲烷、三氯化铁混合,搅拌均匀,取上清液,得到混合溶液;(2)、线性聚苯乙烯材料的交联改性:在不停地搅拌下,将线性聚苯乙烯材料加入步骤(1)所得的混合溶液中,0~60℃反应10 min~48 h;反应结束后,将产物分别用水和乙醇冲洗,干燥,得到交联聚苯乙烯材料。本发明方法步骤简单、条件温和、反应快、安全可控;得到的高度交联聚苯乙烯材料保持了线性聚苯乙烯材料的原始形貌,是理想的碳材料前驱体。
Description
技术领域
本发明属于线性聚苯乙烯改性技术领域,具体涉及一种维持线性聚苯乙烯材料原始形貌的交联改性方法。
技术背景
聚苯乙烯具有优异的化学、热稳定性和机械性能。由于其易加工性,常被制备成不同维度、尺寸的材料,并广泛应用于微滤、纳滤、吸附、油水分离和复合材料领域。此外,聚苯乙烯的超高碳含量(92.4%),使其成为理想的碳材料前驱体。
然而,线性聚苯乙烯的应用极大地受到低交联度的限制。线性聚苯乙烯极易溶解在大多数极性有机试剂中(如甲苯和氯仿等),这会严重破坏材料原有微观结构及形貌,大大限制了聚苯乙烯的应用领域;在高温下发生彻底分解,无法得到碳材料。因此,交联是聚苯乙烯材料在有机溶剂环境应用以及作为前驱体制备碳材料的关键。目前使用的交联方法主要有两种:一种是交联剂与单体共聚交联法,即在苯乙烯聚合制备过程中,通过交联剂(如二乙烯基苯)与苯乙烯单体共聚制备交联聚苯乙烯;但是,交联的聚苯乙烯会丧失可加工性,难以得到形态精确调控的纳米交联聚苯乙烯材料。另一种方法是对已成型的线性聚苯乙烯进行超交联。例如,通过Friedel-Craft反应在聚苯乙烯分子链之间构建交联桥来实现交联。但是Friedel-Craft反应所需要使用的极性有机溶剂对线性聚苯乙烯具有非常强的溶解性,导致预先形成的形貌与结构被完全破坏。
近年来,为了保持线性聚苯乙烯材料形貌实现其交联,一种包含预交联、超交联的两步交联策略被提出(Adv. Mater. 2017, 29, 27)。首先,线性聚苯乙烯材料在由不良溶剂(冰醋酸)构成的交联反应体系中形成低交联结构,使其在极性有机溶剂中稳定存在,形貌与结构不被破坏;然后,再通过超交联反应进一步提升交联度。然而,该种方法存在以下问题:(1)预交联步骤中,溶剂(冰醋酸)与催化剂(氯化铁)的高度络合大大降低了预交联反应速率、延长了反应时间;(2)高达80℃的反应温度使聚合物分子链在溶剂中剧烈运动,发生严重的收缩和粘连现象,影响微观形貌与结构;(3)方法步骤复杂,周期长。因此,亟需一种简便有效的低温、快速交联策略,在维持线性聚苯乙烯材料原始形貌与结构的同时大大提高交联度,以此来拓展聚苯乙烯的应用领域和制备精确形貌的微纳米碳材料。
发明内容
本发明的目的旨在提供一种维持线性聚苯乙烯材料原始形貌的交联改性方法,该方法步骤简单、条件温和、反应快、安全可控;得到的高度交联聚苯乙烯材料保持了线性聚苯乙烯材料的原始形貌,是理想的碳材料前驱体。
为实现上述目的,本发明采取的技术方案如下:
一种维持线性聚苯乙烯材料原始形貌的交联改性方法,步骤如下:
(1)、混合溶液的配制:在室温下,将正己烷、二乙氧基甲烷、三氯化铁混合,搅拌均匀,取上清液,得到混合溶液;
(2)、线性聚苯乙烯材料的交联改性:在不停地搅拌下,将线性聚苯乙烯材料加入步骤(1)所得的混合溶液中,0~60 ℃反应10 min~48 h;反应结束后,将产物分别用水和乙醇冲洗,干燥,得到交联聚苯乙烯材料。
较好地,步骤(1)中,以体积质量比计,正己烷∶二乙氧基甲烷∶三氯化铁=(20~60)mL∶(2~5)mL∶(0.4~3)g。
较好地,步骤(1)和(2)中,混合溶液的配制与交联改性的过程(指两处涉及的反应)均在封闭体系中进行。
较好地,步骤(2)中,所述线性聚苯乙烯材料为线性聚苯乙烯空心纤维膜、线性聚苯乙烯微球或线性聚苯乙烯薄膜(微米厚度)。线性聚苯乙烯空心纤维膜可参考现有技术制备:Minxin Zhang, et al. Fabrication of polystyrene fibers with tunable co-axial hollow tubing structure for oil spill cleanup. Applied Surface Science367 (2076) 126-133。
本发明中,所使用的正己烷不溶三氯化铁,但三氯化铁可以同二乙氧基甲烷络合,二乙氧基甲烷与正己烷互溶,故三者形成均匀的混合溶液反应体系;正己烷为聚苯乙烯的不良溶剂,在较低的反应温度下聚苯乙烯分子链不易运动,因此在交联反应过程中可以维持聚苯乙烯材料的原始形貌;正己烷与三氯化铁极弱的结合保证了三氯化铁极高的催化活性,在较低温度下具有高的反应速率,短时间内形成高的交联密度。因此,得到的交联聚苯乙烯材料在高温、强溶剂下具有好的稳定性,是一种极好的碳前驱体材料。
本发明相对于现有技术,有以下优点:
本发明提供了一种对线性聚苯乙烯材料进行交联改性的方法,并可以维持线性聚苯乙烯在各层次上的原始形貌;该方法不仅过程简单、条件温和、反应时间短、安全可控、原料价格低,而且得到的交联产物在强溶剂下具有好的稳定性,是制备各种形貌结构碳材料的理想前驱体。与交联剂共聚法相比,得到的交联聚苯乙烯材料形貌更为广泛;与常规超交联方法相比,可以完全避免聚苯乙烯材料在超交联过程中的形貌破坏;与逐步交联法相比,过程更简单,成本更低廉,条件更温和,形貌维持更完美;本发明为拓展不同形貌的聚苯乙烯材料的应用领域和制备相应精准形貌的纳米碳材料找到一个切实可行的方案。
附图说明
图1:实施例1线性聚苯乙烯空心纤维膜(a,b)和目标产物FESEM照片(c,d)。
图2:实施例1目标产物的光学显微镜照片。
图3:实施例1线性聚苯乙烯空心纤维膜(a)和目标产物(b)的数码照片。
图4:实施例1目标产物在二氯乙烷浸泡1 h再干燥后的数码照片(a)和FESEM照片(b,c)。
图5:实施例1线性聚苯乙烯空心纤维膜(a)与目标产物(b)的FT-IR谱图。
图6:实施例1目标产物经超交联、700 ℃碳化后产物的FESEM照片。
图7:实施例2目标产物的FESEM照片。
图8:实施例3线性聚苯乙烯旋涂薄膜(a)和目标产物(b)的数码照片。
图9:对照例1目标产物的FESEM照片。
具体实施方式
下面结合具体实施例对本发明的技术方案作进一步解释说明,但本发明的保护范围并不局限于此。
实施例1
一种维持线性聚苯乙烯材料原始形貌的交联改性方法,步骤如下:
(1)、混合溶液的配制:将40 mL正己烷、5 mL二乙氧基甲烷和2 g三氯化铁依次加入100 mL的烧杯中,用保鲜膜密封,在室温下搅拌混合10 min,搅拌结束后,取上清液得到混合溶液;
(2)、线性聚苯乙烯空心纤维膜的交联改性:将线性聚苯乙烯空心纤维膜夹在两层聚乙烯网之间固定,放入步骤(1)所得的混合液中,在30℃下搅拌反应1 h,反应结束后,将产物分别用水和无水乙醇清洗,干燥后即得目标产物。
线性聚苯乙烯空心纤维膜(a,b)和目标产物(c,d)的FESEM照片见图1。图1显示:交联后,纤维空心结构得到了很好的保持。目标产物的光学显微镜照片见图2。图2显示:交联改性后的聚苯乙烯空心纤维维持了原线性聚苯乙烯空心纤维的疏松、长直结构,大尺寸范围内仍然维持着此结构特征。图1和图2都表明本发明方法可以在微观层次上维持前驱体的形貌与结构。
线性聚苯乙烯空心纤维膜(a)和目标产物(b)的数码照片见图3。图3显示:交联前后,膜的尺寸和形态未发生变化,很好地维持了原始宏观形貌,这归因于空心纤维形貌与结构的保持。
目标产物在二氯乙烷中浸泡1 h再干燥后的数码照片(a)和FESEM照片(b,c)见图4。结果表明:交联改性后的聚苯乙烯空心纤维膜的形貌、微观结构没有发生变化。证明本发明交联改性方法所得产物具有高的交联密度,在强溶剂下具有非常好的稳定性。
线性聚苯乙烯空心纤维膜(a)和目标产物(b)的FT-IR谱图见图5。交联后,-CH2-伸缩振动峰(2923~2851 cm-1)强度相对于=C-H伸缩振动峰(3026~3060 cm-1)明显增强,证明苯环上的C-H键被大量取代;单取代苯环的特征峰(1667~2000 cm-1)发生明显改变,进一步证明了交联改性的成功。
目标产物经超交联(超交联方法参考文献Appl. Surf. Sci. 2018, 443, 367)、700 ℃碳化2 h后产物的FESEM照片见图6。结果表明:碳纤维保持了交联聚苯乙烯空心纤维膜的空心结构,以及纤维的疏松、长直结构。这证明,本发明方法改性的聚苯乙烯纳米材料具有高的交联密度(如图4),实现了超交联过程中形貌的维持以及形貌复制碳材料的制备。
实施例2
与实施例1的不同之处在于:将步骤(2)中的“线性聚苯乙烯空心纤维膜”改为“线性聚苯乙烯纳米微球(1 g)”,直接将线性聚苯乙烯纳米微球加入步骤(1)所得的混合溶液中,60 ℃反应48 h;其余步骤同实施例1。
目标产物的FESEM照片见图7。图7显示:交联后,线性聚苯乙烯纳米微球的球形得到很好的维持,防止了球的变形与粘连,表明本发明方法成功实现了线性聚苯乙烯纳米微球的交联改性。
实施例3
与实施例1的不同之处在于:将步骤(2)中的“线性聚苯乙烯空心纤维膜”改为“线性聚苯乙烯旋涂薄膜”,直接将线性聚苯乙烯旋涂薄膜放置在步骤(1)所得的混合溶液中,0℃反应24 h;其余步骤同实施例1。
线性聚苯乙烯旋涂薄膜(a)和目标产物(b)的数码照片见图8。图8显示:交联后,交联聚苯乙烯薄膜维持了线性聚苯乙烯旋涂膜的形貌与完整性。
实施例4~9
与实施例1的不同之处在于:分别将步骤(2)中的反应温度改为0 ℃,10 ℃,20℃,40 ℃,50 ℃,60 ℃;其余步骤同实施例1。
实施例10~16
与实施例1的不同之处在于:分别将步骤(2)中的反应时间改为15 min,30 min,2h,4 h,8 h,24 h,48 h;其余步骤同实施例1。
对照例1
与实施例1的不同之处在于:采用了预交联的方案,即在烧杯中加入40 mL冰醋酸、5.6 mL二乙氧基甲烷和10 g三氯化铁,进行搅拌加热;恒温水浴温度达到80 ℃时,放入线性聚苯乙烯空心纤维膜,恒温反应1 h;反应结束后,将产物分别用水和无水乙醇清洗、干燥,即得目标产物。
目标产物的SEM照片见图9。图9显示:该方法交联得到的交联聚苯乙烯空心纤维膜发生了明显的纤维形变与纤维间的粘连,表明此交联方法不能维持其原始形貌。
Claims (2)
1.一种维持线性聚苯乙烯材料原始形貌的交联改性方法,其特征在于,步骤如下:
(1)、混合溶液的配制:在室温下,将正己烷、二乙氧基甲烷、三氯化铁混合,搅拌均匀,取上清液,得到混合溶液;其中,以体积质量比计,正己烷∶二乙氧基甲烷∶三氯化铁=(20~60)mL∶(2~5)mL∶(0.4~3)g
(2)、线性聚苯乙烯材料的交联改性:在不停地搅拌下,将线性聚苯乙烯材料加入步骤(1)所得的混合溶液中,0~60 ℃反应10 min~48 h;反应结束后,将产物分别用水和乙醇冲洗,干燥,得到交联聚苯乙烯材料;所述线性聚苯乙烯材料为线性聚苯乙烯空心纤维膜、线性聚苯乙烯微球或线性聚苯乙烯薄膜。
2.如权利要求1所述的维持线性聚苯乙烯材料原始形貌的交联改性方法,其特征在于:步骤(1)和(2)中,混合溶液的配制与交联改性的过程均在封闭体系中进行。
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