CN106833093A - 一种光固化疏水树脂改性纳米二氧化硅的制备方法 - Google Patents

一种光固化疏水树脂改性纳米二氧化硅的制备方法 Download PDF

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CN106833093A
CN106833093A CN201611063983.9A CN201611063983A CN106833093A CN 106833093 A CN106833093 A CN 106833093A CN 201611063983 A CN201611063983 A CN 201611063983A CN 106833093 A CN106833093 A CN 106833093A
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silicon dioxide
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姚伯龙
孙常青
李洪萍
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Jiangnan University
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Abstract

本发明涉及一种光固化疏水树脂改性纳米二氧化硅的制备方法,包括如下步骤:将纳米二氧化硅分散于无水乙醇中,在50℃加热搅拌及酸性条件下,与硅烷偶联剂反应4h,将产物洗涤、干燥并重新分散于丙酮中待用;在催化剂及45℃加热搅拌下,将多异氰酸酯与三羟基多元醇反应2.5h得到产物(A);升温至70℃,加入单羟基氟醇,反应2h得到产物(B);保持70℃,加入同时含有‑OH和‑C=C基团的单体,反应2h得到产物(C);将改性纳米二氧化硅丙酮分散液置于70℃下搅拌,滴加产物(C),反应4h;反应结束后洗涤、干燥,即得到设计的光固化疏水树脂改性纳米二氧化硅。

Description

一种光固化疏水树脂改性纳米二氧化硅的制备方法
技术领域
本发明涉及一种光固化疏水树脂改性纳米二氧化硅的制备方法,属于功能性纳米材料领域。
背景介绍
纳米材料是当下应用广泛的一种填充材料,其可有效提高材料的物理化学性能。纳米二氧化硅是其中一种用途广泛的无机化工材料,由于其耐紫外线并能提高其他材料的抗老化、强度及耐化学等性能,因此在涂料等领域有独特的应用。对纳米二氧化硅粒子进行表面修饰改性,接枝功能性基团使其获得特定功能,并作为改性材料与树脂等基体材料复合,可获得性能优异的改性多功能材料。采用纳米级二氧化硅、硅烷偶联剂、异佛尔酮二异氰酸酯(IPDI)、三羟甲基丙烷(TMP)、十三氟辛醇、季戊四醇三丙烯酸酯(PETA)、甲基丙烯酸羟乙酯(HEMA)等单体制得的改性纳米二氧化硅与普通二氧化硅相比,粒子表面的含氟链段使纳米二氧化硅具有优异的超疏水性能,同时粒子表面接有大量双键,应用于光固化材料时可有效加强纳米粒子的稳定性,在光固化材料领域具有良好的应用前景。
发明内容
本发明涉及一种光固化疏水树脂改性纳米二氧化硅的制备方法,其目的在于提供一种利用纳米级二氧化硅、硅烷偶联剂、光固化含氟树脂改性合成的具有光固化及超疏水特性的改性纳米二氧化硅。在该纳米粒子中,粒子表面的含氟链段使得改性粒子具有优异的超疏水性能,同时改性粒子表面具有大量双键基团,使改性纳米二氧化硅粒子同时具备了光固化特性,在应用于光固化材料领域时可有效加强粒子的稳定性。
本发明的技术方案是:
光固化疏水树脂改性纳米二氧化硅的制备方法,包括如下步骤:
(1)将计量的纳米二氧化硅置于干燥洁净的三口烧瓶中,加入150倍质量的无水乙醇,超声使纳米二氧化硅均匀的分散于无水乙醇中;
(2)将分散好的分散液置于50℃水浴锅中,加入计量的经乙酸或其它酸类调节的酸性水(pH值范围为4~5),搅拌10min;继续加入0.2倍纳米二氧化硅计量的含氨基硅烷偶联剂,反应4h;
(3)第一阶段反应结束后,洗涤、干燥制得的改性纳米二氧化硅粒子,并重新分散于丙酮中;
(4)以摩尔份数计,将0.015份摩尔重量的IPDI加入干燥洁净的四口烧瓶中,加入金属有机化合物类催化剂及少量溶剂,通入氮气保护,室温下搅拌均匀;
(5)将上述四口烧瓶置于油浴锅中,升温至45℃,加入0.005份摩尔重量经溶剂溶解的三羟基多元醇,持续搅拌,反应2.5h;
(6)到达反应时间后,向体系中继续加入0.005份摩尔重量的单羟基氟醇,并升温至70℃,反应2h;
(7)到达反应时间后,向体系中继续加入0.005份摩尔重量的含羟基且含大量双键的功能单体,反应2h;
(8)将步骤(3)所得改性纳米二氧化硅丙酮分散液置于70℃油浴锅中,接入冷凝管、搅拌装置,持续搅拌,将步骤(7)所得树脂置于滴液漏斗中,以2s每滴的速度滴入改性纳米二氧化硅丙酮分散液中,反应4h;
(9)反应结束后洗涤、干燥,即得到设计的光固化疏水树脂改性纳米二氧化硅。
具体实施方式
实施例1
将1.8g SiO2、270g无水乙醇加入洁净的三口烧瓶中,超声0.5h分散均匀,将分散液置于50℃恒温水浴锅中,接入搅拌器,加入5ml酸性水,搅拌10min;
向分散体系中加入0.36g Kh550,持续搅拌,反应4h;
将制备的样品洗涤、干燥,并重新分散于丙酮中;
将0.01g催化剂DBTDL、3.34gIPDI加入洁净的四口烧瓶中,插入氮气导管、搅拌棒,搅拌5分钟,将烧瓶置于45℃油浴锅中,利用恒压滴液漏斗将溶解于N,N-二甲基甲酰胺的0.67gTMP以2s每滴的速度缓慢加入到四口烧瓶中,持续搅拌反应2.5h;
将油浴锅升温至70℃,将1.835g十三氟辛醇加入烧瓶,持续搅拌反应2h;
利用恒压滴液漏斗继续将1.49gPETA以2s每滴的速度滴加到反应体系中,持续搅拌反应2h,得到改性疏水树脂;
将改性纳米二氧化硅丙酮分散液置于70℃油浴锅中,接入冷凝管、搅拌装置,持续搅拌,将所得改性疏水树脂置于滴液漏斗中,以2s每滴的速度滴入改性纳米二氧化硅丙酮分散液中,反应4h;
反应结束后洗涤、干燥,即得到设计的光固化疏水树脂改性纳米二氧化硅。

Claims (2)

1.一种光固化疏水树脂改性纳米二氧化硅的制备方法,其特征步骤为:
(1)将计量的纳米二氧化硅置于干燥洁净的三口烧瓶中,加入150倍质量的无水乙醇,超声使纳米二氧化硅均匀的分散于无水乙醇中;
(2)将分散好的分散液置于50℃水浴锅中,加入计量的经乙酸或其它酸类调节的酸性水(pH值范围为4~5),搅拌10min;继续加入0.2倍纳米二氧化硅计量的含氨基硅烷偶联剂,反应4h;
(3)第一阶段反应结束后,洗涤、干燥制得的改性纳米二氧化硅粒子,并重新分散于丙酮中;
(4)以摩尔份数计,将0.015份摩尔重量的IPDI加入干燥洁净的四口烧瓶中,加入金属有机化合物类催化剂及少量溶剂,通入氮气保护,室温下搅拌均匀;
(5)将上述四口烧瓶置于油浴锅中,升温至45℃,加入0.005份摩尔重量经溶剂溶解的三羟基多元醇,持续搅拌,反应2.5h;
(6)到达反应时间后,向体系中继续加入0.005份摩尔重量的单羟基氟醇,并升温至70℃,反应2h;
(7)到达反应时间后,向体系中继续加入0.005份摩尔重量的含羟基且含大量双键的功能单体,反应2h;
(8)将步骤(3)所得改性纳米二氧化硅丙酮分散液置于70℃油浴锅中,接入冷凝管、搅拌装置,持续搅拌,将步骤(7)所得树脂置于滴液漏斗中,以2s每滴的速度滴入改性纳米二氧化硅丙酮分散液中,反应4h;
(9)反应结束后洗涤、干燥,即得到设计的光固化疏水树脂改性纳米二氧化硅。
2.如权利要求1所述的一种光固化疏水树脂改性纳米二氧化硅的制备方法,其特征在于:步骤(1)中所述的纳米二氧化硅为气相二氧化硅、水解二氧化硅、二氧化硅乙醇分散液中的至少一种;
步骤(2)中所述硅烷偶联剂包括所有含氨基的硅烷偶联剂;
步骤(5)中所述三羟基多元醇包括所有含三个羟基基团的多元醇;
步骤(6)中所述氟醇包括所有单羟基氟醇;
步骤(7)中所述含羟基且含大量双键的功能单体为甲基丙烯酸羟乙酯(HEMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。
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