CN108568219B - 复合结构 - Google Patents
复合结构 Download PDFInfo
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- CN108568219B CN108568219B CN201810188762.7A CN201810188762A CN108568219B CN 108568219 B CN108568219 B CN 108568219B CN 201810188762 A CN201810188762 A CN 201810188762A CN 108568219 B CN108568219 B CN 108568219B
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Abstract
一种复合结构,包括:载体;活性层,包覆载体;树枝状分子,通过共价键接枝到活性层;以及多个抗污基团,各自通过共价键接枝到树枝状分子的多个末端。上述树枝状分子的末端具有胺基、羟基或硫醇基。
Description
技术领域
本发明涉及抗污的复合结构,具体涉及采用树枝状分子提高抗污分子的接枝率。
背景技术
抗污水处理膜、免清洗隐形眼镜、抗垢渔具、长寿命水下机具、防藤壶成长的船舶涂漆等产品,是未来产品加值化、低能耗、及资源永续利用相当重要的一环。举例来说,箱网养殖用的渔网,长时间浸泡在海水中,网目容易成长海洋生物,使渔网变重,阻塞造成海水无法交换,导致高密度养殖下,其水中氧气交换量不足,且网目上的贝类会割伤鱼类,造成细菌感染,导致鱼类死亡。
因此,抗污的机能性处理,在水下制具的应用是非常重要的。化学改性方法主要是将抗污分子接枝或涂布在产品表面,使其产品表面对污染物的亲水性或水合能力或空间位阻的能力增加,来达到抗污的效果。利用表面化学改性的方法制作抗污材料在这些产品上常遇到两大问题:(1)直接将抗污分子接枝在需要进行抗污处理的产品上时,产品表面可供进行抗污材料改质的接枝点有限,导致接枝后的抗污材料覆盖率明显不足,使得抗污能力大受影响。(2)将抗污材料直接涂布在产品表面,可提升覆盖率,但其与产品的黏着力不佳,容易被水流冲走而剥落,且部分产品应用会有涂布层过厚,水阻太大,效能下降的问题。
综上所述,目前亟需新的方法将抗污分子大量接枝在产品表面,以提升产品的抗污能力。
发明内容
本发明一实施例提供的复合结构,包括:载体;活性层,包覆载体;树枝状分子,通过共价键接枝到活性层;以及多个抗污基团,各自通过共价键接枝到树枝状分子的多个末端。
附图说明
图1为本发明实施例中复合结构的示意图;
【附图元件说明】
11-载体;13-活性层;
15-树枝状分子;17-抗污基团。
具体实施方式
本发明一实施例提供的复合结构如图1所示,其包括载体11;活性层13,包覆载体11;树枝状分子15,通过共价键接枝到活性层13;以及多个抗污基团17,各自通过共价键接枝到树枝状分子15的多个末端。在图1所示的实施例中,树枝状分子15的末端为胺基,其与活性层13的表面的酰氯基反应以形成酰胺键。可以理解的是,图1中的键结仅用以举例,其可依树枝状分子15的末端的官能基与活性层13其表面上的基团而改变,并不限于图1所示的酰胺键。此外,图1中的树枝状分子15仅具有5个末端胺基,但树枝状分子15可具有数十个胺基,视结构而定。
在本发明的一些实施例中,载体11包括有机纤维或无机纤维的无纺布或再通过相转换工艺或电纺工艺所得的复合滤膜。在本发明的一些实施例中,上述复合滤膜的孔洞尺寸介于5nm至5μm之间。若孔洞尺寸过大,在制作活性层13会造成破孔导致膜无过滤功能。若孔洞尺寸过小,则滤膜的水阻过大,渗透水量过低。
在本发明的一些实施例中,有机纤维包括聚纤维素酯、聚砜、聚醚砜、聚丙烯、聚醚酮、聚酯如聚对苯二甲酸乙二醇酯、聚亚酰胺、氯化聚氯乙烯、聚偏二氟乙烯或苯乙烯-丙烯腈共聚物。在本发明的一些实施例中,无机纤维包括碳纤维、玻璃纤维或金属纤维。当载体11为上述纤维形成的网状层时,复合结构可作为滤膜以滤除水中盐类。
在本发明的一些实施例中,活性层13由(a)多元醇、多元硫醇、多元胺或上述的组合与(b)多酰卤基化合物、酸酐化合物、多羧酸基化合物、多烯基化合物、多炔基化合物、多卤化合物或多环氧基化合物反应而成。在本发明的一些实施例中,可将载体11浸泡至(a)多元醇、多元硫醇、多元胺或上述的组合的水相溶液中,使载体11中的纤维表面附着(a)化合物。在本发明的一些实施例中,含有(a)化合物的水相溶液中,(a)化合物的浓度介于0.05wt%至5wt%之间。若(a)化合物的浓度过低,则界面交联层太薄,结构刚性较差且脱盐效率不足。若(a)化合物的浓度过高,则界面交联层太厚,膜材水阻大,产水量低。
接着将载体11浸泡至(b)多酰卤基化合物、酸酐化合物、多羧酸基化合物、多烯基化合物、多炔基化合物、多卤化合物或多环氧基化合物的有机相溶液中,使(a)化合物与(b)化合物在水相/有机相的界面产生界面交联反应。在本发明的一些实施例中,含有(b)化合物的有机相溶液中,(b)化合物的浓度介于0.01wt%至1wt%之间。若(b)化合物的浓度过低,则界面交联层太薄,结构刚性较差且脱盐效率不足。若(b)化合物的浓度过高,则界面交联层太厚,膜材水阳大,产水量低。在本发明的一些实施例中,(a)化合物可采用哌嗪(具有两个胺基),而(b)化合物可采用1,3,5-苯三甲酰氯(具有三个酰氯基)。
在图1中,活性层13覆盖载体11的表面。但在载体11为纤维组成的网状物如滤材时,活性层13包覆载体11中的纤维表面。换言的,活性层13包覆载体11其与活性层13接触的部份。活性层的作用之一为阻挡水中离子,达到除盐作用;另一作用是形成活性位置,使树枝状抗污分子可接着于滤膜表面。
上述(a)化合物与(b)化合物的反应残留部份酰卤基、酸酐基、羧酸基、烯基、炔基、卤基或环氧基,以与树枝状分子15其末端的胺基、羟基或硫醇基反应形成共价键。在本发明的一些实施例中,树枝状分子15包括聚乙烯亚胺、末端改质有羟基的聚乙烯亚胺、末端改质有硫醇基的聚乙烯亚胺、聚酯、末端改质有羟基的聚酯、末端改质有硫醇基的聚酯、聚酰胺-胺、末端改质有羟基的聚酰胺-胺、末端改质有硫醇基的聚酰胺-胺或末端具有胺基、羟基或硫醇基的其他合适树枝状分子。在本发明的一些实施例中,树枝状分子15的重均分子量介于100Da至100kDa之间。若树枝状分子的重均分子量过高,则溶解度不佳,无法进行修饰反应。若树枝状分子的重均分子量过低,则滤膜水通道阻塞,造成产水通量降低。
在本发明的一些实施例中,抗污基团17包括磺酸甜菜碱、羧基甜菜碱、磷酸酯甜菜碱、聚乙二醇、2-羟基乙基、聚乙烯醇或其他合适的抗污基团。上述抗污基团17的结构可参考Polymer Journal(2014)46,436-443。在本发明的一些实施例中,抗污基团17接枝到树枝状分子15末端的方法如下。首先采用抗污分子,其抗污基团键结至反应基团如丙烯酸酯基、乙烯基、环氧基、卤素、羟基或硫醇基。接着将抗污分子与树枝状分子混合反应,使树枝状分子末端的胺基、羟基或硫醇基与抗污分子的反应基团进行加成反应(丙烯酸酯基、乙烯基或环氧基)、取代反应(卤素)、脱水反应(羟基)或脱硫醇反应(硫醇)。在本发明的一些实施例中,抗污基团的重均分子量介于50Da至2000Da之间。若抗污基团的分子量过大,则反应产物容易形成团聚现象,改质效果不佳。若抗污基团的分子量过小,则反应产物抗污效果不佳。在本发明的一些实施例中,抗污分子可为[3.(甲基丙烯酰胺基)丙基]二甲基(3.硫代丙基)氢氧化铵或[2.(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵,上述两者的抗污基团属于磺酸甜菜碱基。
在本发明的一些实施例中,可先取抗污分子与树枝状分子15反应后,再使树枝状分子15残留的胺基、羟基或硫醇基与活性层13的酰卤基、酸酐基、羧酸基、烯基、炔基、卤基或环氧基进行反应。在此实施例中,树枝状分子的末端官能基与抗污分子的摩尔比介于1∶0.1至1∶0.8之间。若抗污分子的比例过低,则最后形成的复合结构表面的抗污基团不足。若抗污分子的比例过高,则树枝状分子的所有末端官能基将改质为抗污基团,而无多余官能基与活性层13的酰卤基、酸酐基、羧酸基、烯基、炔基、卤基或环氧基进行反应。在此实施例中,可将末端改质有抗污分子的树枝状分子配制成0.01wt%至5wt%的水相溶液,再将活性层13浸入上述水相溶液。若末端改质有抗污分子的树枝状分子的浓度过低,则抗污效果不显著。若末端改质有抗污分子的树枝状分子的浓度过高,则材料使用效率太低。在另一实施例中,可先取树枝状分子15与活性层13的酰卤基、酸酐基、羧酸基、烯基、炔基、卤基或环氧基进行反应后,再取抗污分子与树枝状分子15的胺基、羟基或硫醇基反应。
若省略树枝状分子15,直接将抗污分子接枝到活性层13上,则抗污分子的接枝量不足,无法有效提升复合结构的抗污效果。本发明实施例采用树枝状分子15,可有效提升活性层13上的抗污分子接枝量(即抗污基团17的比例)。
为了让本发明的上述和其他目的、特征和优点能更明显易懂,下文特举数实施例配合所附图示,作详细说明如下:
实施例
比较例1
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材中的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,以形成活性层(聚酰胺)于滤材上。将上述结构泡入水中,使未反应的酰氯基与水反应形成羧酸基。风干上述结构45s后以得纤维表面包覆有活性层的滤材,其表面具有羧酸基。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量下降至初始通量的89.48%。过滤25h后,上述滤膜的排盐率为96.19%。
实施例1-1
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1Wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取0.2g的聚乙烯亚胺(PEI)(重均分子量25kDa,Sigma-Aldrich 408727-100ML,polyethylenimine,branched)作为树枝状分子。取0.65g的[2-(甲基丙烯酰胺基)丙基]二甲基(3-硫代丙基)氢氧化铵(MEDSA,Sigma-Aldrich 537284-50G,[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide)作为抗污分子,其具有磺酸甜菜碱的基团。将两者加入水中,并加入催化剂0.065g K2S2O8与0.022g的Na2S2O5并于50℃下搅拌2h,之后在常温下(25℃)静置一晚,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。经上述反应后,形成末端具有抗污基团的树枝状分子(PEI-MEDSA)。上述反应如式1所示:
在式1中,D为PEI的核心,n为PEI改质前的末端胺基数目,x为接枝到PEI的MEDSA数目,而y为PEI改质后保留的胺基数目。
接着将具有活性层包覆纤维的滤材,浸入0.2wt%的PEI-MEDSA的水相溶液中1min,使PEI-MEDSA的胺基与活性层上残留的酰氯基反应。上述反应如式2所示:
在式2中,若y=1,则与活性层的酰氯基反应后的树枝状分子将不残留任何胺基。经X射线光电子能谱(XPS)分析上述滤膜表面,其S原子百分比大幅增加,可确认上述工艺可将具有抗污基团的树枝状分子接枝到活性层表面。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的93.31%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达97.44%。与比较例1相较,实施例1-1的滤膜在长时间使用后具有较佳的稳定性与排盐率。
实施例1.2
与实施例1-1类似,差别在于将重均分子量为25k的PEI置换为800的PEI(重均分子量800Da,Sigma-Aldrich 408719-100ML,polyethylenimine,branched)。其他形成活性层、形成PEI-MEDSA、以及取活性层与PEI-MEDSA反应的步骤均与实施例1-1类似。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的103.4%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达97.81%。与比较例1相较,实施例1-2的滤膜在长时间使用后具有较佳的稳定性与排盐率。
比较例2-1
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。将上述结构泡入水中,使未反应的酰氯基与水反应形成羧酸基。风干上述结构45s后以得纤维表面包覆有活性层的滤材,其表面具有羧酸基。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量下降至初始通量的66.7%。过滤25h后,上述滤膜的排盐率为97.80%。
比较例2-2
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材中的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取ZWAEM的梳状高分子,其侧链具有抗污基团(MEDSA与AEM的共聚物)(AEM,Sigma-Aldrich,516155-5G,2-Aminoethyl methacrylate hydrochloride)。接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的ZWAEM的水相溶液中3min,使ZWAEM的胺基与活性层上残留的酰氯基反应。上述反应如式3所示:
经XPS分析上述滤膜表面,其S原子百分比大幅增加,可确认上述工艺可将具有抗污基团的梳状高分子接枝到活性层表面。应理解的是,在式3中活性层上残留的酰氯基数目(1个)仅为示意,实际上活性层可具有多个残留的酰氯基。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量大幅下降至初始通量的53.80%。过滤25h后,上述滤膜的排盐率为96.98%。
实施例2-1
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材中的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取0.2g的聚乙烯亚胺(PEI)(重均分子量25kDa,Sigma-Aldrich 408727-100ML,polyethylenimine,branched)作为树枝状分子。取0.65g的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵(MEDSA)作为抗污分子,其具有磺酸甜菜碱基。将两者加入水中并加入催化剂0.065g K2S2O8与0.022g的Na2S2O5并于50℃下搅拌2h,之后在常温下(25℃)静置一晚,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。经上述反应后,形成末端具有抗污基团的树枝状分子(PEI-MEDSA)。上述反应如式4所示:
在式4中,D为PEI的核心,n为PEI改质前的末端胺基数目,x为接枝到PEI的MEDSA数目,而y为PEI改质后保留的胺基数目。
接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的PEI-MEDSA的水相溶液中1min,使PEI-MEDSA的胺基与活性层上残留的酰氯基反应。上述反应如式5所示:
在式5中,若y=1,则与活性层的酰氯基反应后的树枝状分子将不残留任何胺基。经XPS分析上述滤膜表面,其S原子百分比大幅增加,可确认上述工艺可将具有抗污基团的树枝状分子接枝到活性层表面。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的82.7%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达97.45%。与比较例2-1相较,实施例2-1的滤膜在长时间使用后具有较佳的稳定性与类似的排盐率。与比较例2-2相较,实施例2-1的滤膜在长时间使用后具有较佳的稳定性与排盐率。
实施例2-2
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材中的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取0.2g的聚乙烯亚胺(PEI)(重均分子量25kDa,Sigma-Aldrich 408727-100ML,polyethylenimine,branched)作为树枝状分子,溶于水中。接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的PEI的溶液中3min,使PEI的胺基与活性层上残留的酰氯基反应。上述反应如式6所示:
接着取0.65g的MEDSA作为抗污分子,将催化剂0.065g K2S2O8与0.022g的Na2S2O5与抗污分子加入上述溶液中并加热至50℃后反应30min,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。经上述反应后,形成的产物与式5的产物类似,在此不赘述。
实施例2-2与实施例2-1的差别在于,先将树枝状分子(PEI)接枝到活性层表面后,再将抗污分子(MEDSA)接枝到树枝状分子的末端。与实施例2-1相较,实施例2-2改质滤膜的方法较耗时。至于实施例2-2的滤膜特性如稳定性与排盐率,则与实施例2-1的滤膜类似。
实施例3(AF1与AF2)
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材中的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.1wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
AF1的抗污材料的合成方式:取13.4g的聚乙烯亚胺(PEI)(重均分子量800Da,Sigma-Aldrich 408719-100ML,polyethylenimine,branched)作为树枝状分子。取14g的[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵(MEDSA)作为抗污分子,其具有磺酸甜菜碱基。将两者加入水中并加入催化剂3mol%的催化剂(NH4)2Ce(NO3)6反应3h,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。反应结束后溶液会产生沉淀物,通过过滤方式去除。接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的PEI-MEDSA的溶液中3min,使PEI的胺基与活性层上残留的酰氯基反应。
AF2的抗污材料为ZWAEM,是由MEDSA与AEM进行共聚合所得到的梳状抗污高分子,其结构如式7所示:
接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的ZWAEM的溶液中3min,使ZWAEM的胺基与活性层上残留的酰氯基反应。
在实施例3中,滤膜AF1与AF2的过滤面积由原本(活性层包覆纤维表面的滤材)的50cm2增加到0.39m2,过滤面积提升了78倍。
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与1000ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤80h后,上述滤膜AF1的通量仍为初始通量的91.44%,显见其稳定性。过滤80h后,上述滤膜的产水电导率降低到46μS/cm。具有活性层包覆纤维表面的滤材经过80h的过滤后,通量仅剩下初始通量的87.55%。滤膜AF2经过80h的过滤后,通量仅剩下初始通量的87.51%。与滤膜AF2相较,滤膜AF1在长时间使用后具有较佳的稳定性与较佳的排盐率。
实施例4
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.15wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取6.7g的聚乙烯亚胺(PEI)(重均分子量25kDa,Sigma-Aldrich 408727-100ML,polyethylenimine,branched)作为树枝状分子。取12.5g的聚(乙二醇)甲基丙烯酸酯(PEGMA)(数均分子量500Da,Sigma-Aldrich 409529-100ML,Poly(ethylene glycol)methacrylate)作为抗污分子,其具有羟基。将两者加入水中均匀混合10min后,加入催化剂842mg(NH4)2Ce(NO3)6并于50℃下搅拌3h,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。经上述反应后,形成末端具有抗污基团的树枝状分子(PEI-PEG)溶液。反应后溶液中有沉淀物析出,去除沉淀物后得抗污分子溶液。
接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的PEI-PEG的水相溶液中1min,使PEI-PEG的胺基与活性层上残留的酰氯基反应,以将具有抗污基团的树枝状分子接枝到活性层表面。上述PEI-PEG的示意图如下:
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的79.32%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达98.00%。过滤25h后,原始未改质的滤膜的通量为初始通量的66.56%。过滤25h后,原始未改质的滤膜的排盐率为97.59%。与原始未改质的滤膜相较,实施例4的滤膜在长时间使用后具有较佳的稳定性与排盐率。
实施例5
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm~5μm)置入室温下的哌嗪水溶液(1Wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.15wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取1g的超支化BIS-MPA聚酯-64-羟基,4代(HBP-OH,Sigma-Aldrich 686573-10G)作为树枝状分子,溶于100mL的甲醇中。接着将具有活性层包覆纤维表面的滤材,浸入1wt%的HBP-OH溶液中3min,使HBP-OH的羟基与活性层上残留的酰氯基反应。
接着取1g的丙烯酰氯配置成1wt%的正己烷溶液。将滤膜泡入正己烷溶液中,使树枝状分子末端的羟基与酰氯进行反应以形成双键于树枝状分子末端。接着将滤膜泡入8wt%的MEDSA(抗污分子)水溶液中,再加入催化剂0.4g K2S2O8与0.1g的Na2S2O5并于50℃下搅拌16h,使树枝状分子末端的双键与抗污分子末端的双键进行加成反应,形成末端具有抗污基团的树枝状分子(HBP-OH-MEDSA)。经X射线光电子能谱(XPS)分析上述滤膜表面,其S原子百分比大幅增加,可确认上述工艺可将具有抗污基团的树枝状分子接枝到活性层表面。
上述HBP-OH-MEDSA的示意图如下:
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的89.50%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达98.78%。过滤25h后,原始未改质的膜的通量为初始通量的60.05%。过滤25h后,原始未改质的滤膜的排盐率为97.92%。与原始未改质的滤膜相较,实施例5的滤膜在长时间使用后具有较佳的稳定性与排盐率。
实施例6
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm至5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.15wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
取3.82g的MEDSA作为抗污分子,溶入10mL的水中。接着取1g的三(2-氨乙基)胺(TAEA)(Sigma-Aldrich 225630-10ML,Tris(2-aminoethyl)amine)作为树枝状分子加入MEDSA的水溶液均匀混合2min后,加入催化剂224.8mg(NH4)2Ce(NO3)6并于50℃下搅拌3h,使树枝状分子末端的胺基与抗污分子末端的双键进行加成反应。经上述反应后,形成末端具有抗污基团的树枝状分子(TAEA-MEDSA)溶液。反应后溶液中有沉淀物析出,去除沉淀物后得抗污分子溶液。
接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的TAEA-MEDSA的水相溶液中1min,使TAEA-MEDSA的胺基与活性层上残留的酰氯基反应,以将具有抗污基团的树枝状分子接枝到活性层表面。上述TAEA-MEDSA的示意图如下:
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的97.96%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达98.77%。过滤25h后,原始未改质的膜的通量为初始通量的77.98%。过滤25h后,原始未改质的未改质的滤膜的排盐率为99.08%。与原始未改质的滤膜相较,实施例6的滤膜在长时间使用后具有较佳的稳定性,此外排盐率变化不大。
实施例7
取滤材(新长丰PES膜,膜材孔洞尺寸为5nm~5μm)置入室温下的哌嗪水溶液(1wt%)中1min,使滤材的纤维表面包覆一层哌嗪分子。用滚轮移除滤材上多余的哌嗪水溶液,泡入1,3,5-苯三甲酰氯的己烷溶液(0.15wt%)中1min,使哌嗪与1,3,5-苯三甲酰氯在水相/有机相的界面之间进行交联反应,在滤材上形成活性层。之后风干上述结构45s。上述活性层表面仍有未反应的酰氯基。
此外,取1g的聚乙烯亚胺(PEI)(重均分子量25kDa,Sigma-Aldrich 408727-100ML,polyethylenimine,branched)作为树枝状分子。接着将具有活性层包覆纤维表面的滤材,浸入0.2wt%的PEI溶液中3min,使PEI的羟基与活性层上残留的酰氯基反应。
接着取7g的聚(乙二醇)二丙烯酸酯(PEGDA)(数均分子量700Da,Sigma-Aldrich455008-100ML,Poly(ethylene glycol)diacrylate)与50mL的水配置成14wt%的水溶液。将滤膜泡入PEGDA的水溶液中,再加入164mg的催化剂(NH4)2Ce(NO3)6中反应30min,使树枝状分子PEI末端的胺基与PEGDA的双键进行加成反应,以形成双键于树枝状分子的末端。接着将滤膜取出后以去离子水清洁滤膜表面,再泡入16wt%的MEDSA(抗污分子)水溶液中,并加入催化剂0.8g K2S2O8与0.26g的Na2S2O5并于50℃下反应30min,使树枝状分子末端的双键与抗污分子末端的双键进行加成反应,形成末端具有抗污基团的树枝状分子(PEI-PEGDA-MEDSA)。上述PEI-PEGDA-MEDSA的结构如下:
取上述滤膜过滤配制的水溶液,且水溶液含有2000ppm的硫酸镁与50ppm的牛血清白蛋白(BSA)。上述水溶液流速为1.2L/min,进出压力均为100psi。过滤25h后,上述滤膜的通量仍为初始通量的94.34%,显见其稳定性。过滤25h后,上述滤膜的排盐率仍高达98.85%。过滤25h后,原始未改质的膜的通量为初始通量的77.98%。过滤25h后,原始未改质的滤膜的排盐率为99.08%。与原始未改质的滤膜相较,实施例7的滤膜在长时间使用后具有较佳的稳定性,此外排盐率变化不大。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则的内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围的内。
Claims (8)
1.一种复合结构,包括:
一载体;
一活性层,包覆所述载体;
一树枝状分子,通过共价键接枝到所述活性层;以及
多个抗污基团,各自通过共价键接枝到所述树枝状分子的多个末端,
其中,所述树枝状分子包括聚乙烯亚胺、聚酯或聚酰胺-胺,
其中,所述树枝状分子的重均分子量介于100Da至100kDa之间,以及
所述抗污基团包括磺酸甜菜碱基、羧基甜菜碱基、磷酸酯甜菜碱基、聚乙二醇基、2-羟基乙基或聚乙烯醇基。
2.根据权利要求1所述的复合结构,其中,所述载体包括有机纤维或无机纤维的无纺布。
3.根据权利要求2所述的复合结构,其中,所述有机纤维包括聚纤维素酯、聚砜、聚醚砜、聚丙烯、聚醚酮、聚酯、聚亚酰胺、氯化聚氯乙烯、聚偏二氟乙烯或苯乙烯-丙烯腈共聚物。
4.根据权利要求2所述的复合结构,其中,所述无机纤维包括碳纤维、玻璃纤维或金属纤维。
5.根据权利要求1所述的复合结构,其中,所述树枝状分子的末端具有胺基、羟基或硫醇基。
6.根据权利要求5所述的复合结构,其中,所述活性层由(a)多元醇、多元硫醇、多元胺或上述的组合与(b)多酰卤基化合物、酸酐化合物、多羧酸基化合物、多烯基化合物、多炔基化合物、多卤化合物或多环氧基化合物反应而成,且上述反应残留部份酰卤基、酸酐基、羧酸基、烯基、炔基、卤基或环氧基,以与所述树枝状分子其末端的胺基、羟基或硫醇基反应形成共价键。
7.根据权利要求1所述的复合结构,其中,所述树状分子包括末端改质有羟基的聚乙烯亚胺、末端改质有硫醇基的聚乙烯亚胺、末端改质有羟基的聚酯、末端改质有硫醇基的聚酯、末端改质有羟基的聚酰胺-胺或末端改质有硫醇基的聚酰胺-胺。
8.根据权利要求1所述的复合结构,其中,所述抗污基团的重均分子量介于50Da至2000Da之间。
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