CN108774304A - 改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 - Google Patents
改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 Download PDFInfo
- Publication number
- CN108774304A CN108774304A CN201810666313.9A CN201810666313A CN108774304A CN 108774304 A CN108774304 A CN 108774304A CN 201810666313 A CN201810666313 A CN 201810666313A CN 108774304 A CN108774304 A CN 108774304A
- Authority
- CN
- China
- Prior art keywords
- modified nano
- polyurethane
- epoxy
- nano tio
- composite material
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种改性纳米TiO2/环氧‑聚氨酯三元复合材料的制备方法,包括如下步骤:1)油酸改性纳米TiO2的制备;2)改性纳米TiO2/环氧树脂‑聚氨酯三元复合材料的制备。本发明将油酸改性纳米TiO2表面的羟基与异氰酸酯基团、聚醚和环氧树脂发生逐步聚合反应,经IR、SEM等分析手段表征后成功制得性能优异的改性纳米TiO2/环氧‑聚氨酯三元复合材料;测试结果表明,改性纳米TiO2/环氧‑聚氨酯涂膜稳定性能好,硬度高,耐水性能和力学性能强,抗紫外和抗老化性能亦有明显提高。
Description
技术领域
本发明涉及一种复合材料的制备方法,具体涉及一种改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法。
背景技术
纳米粒子的尺寸约为1到100nm,处于原子簇和凝聚体之间,具有独特的小尺寸效应、表面与界面效应、量子尺寸效应等特性。由于纳米粒子表面非配对原子多,粒径又小,纳米粒子改性后其表面的-OH能与加入的共聚物分子链上的活性基团发生化学反应,因而纳米粒子对聚合物材料能起到很好的改性目的。但由于纳米粒径小,表面活性高,粒子容易发生自身团聚,使聚合物复合材料的拉伸强度、冲击强度等力学性能受到很大的限制。因此,在纳米粒子的应用中,如何避免粒子团聚,是改善复合材料性能的关键。
发明内容
本发明的目的是提供一种改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法,避免纳米粒子团聚和提高聚合物复合材料的拉伸强度、冲击强度等力学性能。
本发明所采用的技术方案是:
一种改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法,包括如下步骤:
1)油酸改性纳米TiO2的制备:
将6~10g钛酸丁酯和0.8~1.2g油酸溶解于30~50mL的无水乙醇中,加入6~10g的Na2SO4·10H2O,磁力搅拌均匀,缓慢升温至60~70℃,氮气保护下反应1~3小时,得到淡黄色悬浊液;将淡黄色悬浊液进行抽滤、洗涤后得到沉淀,将所得沉淀溶解于30~50mL无水乙醇中,再抽滤、洗涤一次,最终将沉淀室温下真空干燥,即得油酸改性纳米TiO2,待用;
2)改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的制备:
将步骤1)中制得的4~6g油酸改性纳米TiO2与30~50mL的丙酮均匀混合,调节pH值为7~8;将其分散液逐滴加入到5~8g的二苯基甲烷二异氰酸酯中,继续加入16~20mL聚醚和1~3滴二月桂酸二丁基锡,然后加入1~1.4mL一缩二乙二醇、10~15mL丙酮和3.4~3.8g二羟甲基丙酸,升温至70~80℃,反应2~3h;继续加入3~5g环氧树脂和2~4滴二月桂酸二丁基锡,50~70℃条件下反应1~3h;最后加入3.4~3.8mL三乙胺和40~60mL去离子水,磁力搅拌,乳化30~50min,脱去丙酮溶剂即得改性纳米TiO2/环氧树脂-聚氨酯三元复合材料。
本发明的有益效果是:
本发明公开的一种改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法,将油酸改性纳米TiO2表面的羟基与异氰酸酯基团、聚醚和环氧树脂(E51)发生逐步聚合反应,得到性能优异的改性纳米TiO2/环氧-聚氨酯三元复合材料;
测试结果表明,改性纳米TiO2/环氧-聚氨酯涂膜稳定性能好,硬度高,耐水性能和力学性能强,抗紫外和抗老化性能亦有明显提高。
下面结合附图对本发明作进一步详细描述。
附图说明
图1为不同复合材料的红外吸收光谱图;
图2为环氧-聚氨酯复合涂膜SEM图;
图3为改性纳米TiO2/环氧-聚氨酯复合涂膜SEM图;
图4为纳米TiO2含量对环氧-聚氨酯复合涂膜力学性能影响曲线图;
图5为环氧树脂含量对复合涂膜的吸水率影响曲线图;
图6为复合涂膜的紫外吸收曲线图。
具体实施方式
为了加深对本发明的理解,下面结合附图和实施例对本发明作进一步详细的说明。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
本发明中,实验药品:钛酸丁酯(分析纯,天津科密欧公司),油酸(分析纯,天津科密欧),环氧树脂(工业纯,巴陵石化公司),二苯基甲烷二异氰酸酯(工业纯,拜耳公司),二羟甲基丙酸(工业纯,安庆中大),丙酮(分析纯,天津富裕公司),三乙胺(分析纯,西陇化工公司);
实验仪器:傅立叶变换红外光谱仪(Perkin-Elmer,美国PE公司),紫外-可见分光光度计(Lambda25,上海天普公司),扫描电子显微镜(JSM-6360LV,日本电子株式会社),QHQ铅笔硬度计(广州蔚仪金相公司),电子拉伸试验机(济南华兴公司),电热真空干燥箱(ZK-82B型,上海实验仪器公司)。
实施例1
1)油酸改性纳米TiO2的制备:
将6g钛酸丁酯和0.8g油酸溶解于30mL的无水乙醇中,加入6g的Na2SO4·10H2O,磁力搅拌均匀,缓慢升温至60℃,氮气保护下反应1小时,得到淡黄色悬浊液;将淡黄色悬浊液进行抽滤、洗涤后得到沉淀,将所得沉淀溶解于30mL无水乙醇中,再抽滤、洗涤一次,最终将沉淀室温下真空干燥,即得油酸改性纳米TiO2,待用;
2)改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的制备:
将步骤1)中制得的4g油酸改性纳米TiO2与30mL的丙酮均匀混合,调节pH值为7;将其分散液逐滴加入到5g的二苯基甲烷二异氰酸酯中,继续加入16mL聚醚和1滴二月桂酸二丁基锡,然后加入1mL一缩二乙二醇、10mL丙酮和3.4g二羟甲基丙酸,升温至70℃,反应2h;继续加入3g环氧树脂和2滴二月桂酸二丁基锡,50℃条件下反应1h;最后加入3.4mL三乙胺和40mL去离子水,磁力搅拌,乳化30min,脱去丙酮溶剂即得改性纳米TiO2/环氧树脂-聚氨酯三元复合材料。
实施例2
1)油酸改性纳米TiO2的制备:
将10g钛酸丁酯和1.2g油酸溶解于50mL的无水乙醇中,加入10g的Na2SO4·10H2O,磁力搅拌均匀,缓慢升温至70℃,氮气保护下反应3小时,得到淡黄色悬浊液;将淡黄色悬浊液进行抽滤、洗涤后得到沉淀,将所得沉淀溶解于50mL无水乙醇中,再抽滤、洗涤一次,最终将沉淀室温下真空干燥,即得油酸改性纳米TiO2,待用;
2)改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的制备:
将步骤1)中制得的6g油酸改性纳米TiO2与50mL的丙酮均匀混合,调节pH值为8;将其分散液逐滴加入到8g的二苯基甲烷二异氰酸酯中,继续加入20mL聚醚和3滴二月桂酸二丁基锡,然后加入1.4mL一缩二乙二醇、15mL丙酮和3.8g二羟甲基丙酸,升温至80℃,反应3h;继续加入5g环氧树脂和4滴二月桂酸二丁基锡,70℃条件下反应3h;最后加入3.8mL三乙胺和60mL去离子水,磁力搅拌,乳化50min,脱去丙酮溶剂即得改性纳米TiO2/环氧树脂-聚氨酯三元复合材料。
实施例3
1)油酸改性纳米TiO2的制备:
将8g钛酸丁酯和1.0g油酸溶解于40mL的无水乙醇中,加入8g的Na2SO4·10H2O,磁力搅拌均匀,缓慢升温至65℃,氮气保护下反应2小时,得到淡黄色悬浊液;将淡黄色悬浊液进行抽滤、洗涤后得到沉淀,将所得沉淀溶解于40mL无水乙醇中,再抽滤、洗涤一次,最终将沉淀室温下真空干燥,即得油酸改性纳米TiO2,待用;
2)改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的制备:
将步骤1)中制得的5g油酸改性纳米TiO2与40mL的丙酮均匀混合,调节pH值为7.5;将其分散液逐滴加入到6.5g的二苯基甲烷二异氰酸酯中,继续加入18mL聚醚和2滴二月桂酸二丁基锡,然后加入1.2mL一缩二乙二醇、12.5mL丙酮和3.6g二羟甲基丙酸,升温至75℃,反应2.5h;继续加入4g环氧树脂和3滴二月桂酸二丁基锡,60℃条件下反应2h;最后加入3.6mL三乙胺和50mL去离子水,磁力搅拌,乳化40min,脱去丙酮溶剂即得改性纳米TiO2/环氧树脂-聚氨酯三元复合材料。
为了进一步检验本发明改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的效果,特举实验例如下:
1)不同材料的红外吸收光谱图
如图1可知,图1中E51、E51-PU、TiO2-E51-PU分别为环氧树脂、环氧-聚氨酯、改性纳米TiO2/环氧-聚氨酯材料的红外吸收光谱图。在E51红外吸收光谱图中,915cm-1处为环氧基团的红外伸缩振动吸收峰。在E51-PU红外吸收光谱图中,2270~2280cm-1处的—NCO吸收峰和3528cm-1处的—OH吸收峰消失,3445cm-1处出现了—N-H基团的红外特征吸收峰,表明羟基和异氰酸酯基团反应完全,生成了氨基甲酸酯。此外,图1中923cm-1处为环氧树脂的端环氧基的红外吸收峰,可见环氧-聚氨酯复合材料中出现了环氧基团,证明环氧树脂已引入聚氨酯分子结构中。在TiO2-E51-PU红外吸收光谱图中,681cm-1处的特征吸收峰为纳米TiO2的红外吸收峰,可见纳米TiO2已经掺入到环氧-聚氨酯复合材料中,得到了稳定的改性纳米TiO2/环氧-聚氨酯复合材料。
2)环氧-聚氨酯复合涂膜SEM分析和改性纳米TiO2/环氧-聚氨酯复合涂膜SEM分析
图2为环氧-聚氨酯复合涂膜SEM图;
图3为改性纳米TiO2/环氧-聚氨酯复合涂膜SEM图;
图3SEM图相较于图2,可以看出环氧-聚氨酯复合涂膜中较均匀地分散了许多纳米粒子。这表明,改性纳米TiO2上的羟基与异氰酸酯基团反应,环氧-聚氨酯分子链上已成功接枝了纳米TiO2粒子,得到了稳定的改性纳米TiO2/环氧-聚氨酯复合涂膜。
3)纳米TiO2含量对环氧-聚氨酯复合涂膜力学性能影响分析
如图4可知,涂膜的断裂伸长率随着TiO2含量的增加而逐渐减小,当TiO2添加量增加到1.0wt%时,其断裂伸长率由最高780%减少到438%,主要原因是由于添加的无机纳米粒子增加了聚合物的交联度,断裂伸长率反而减小。从图4也可以看出,涂膜的拉伸强度一般随着TiO2含量的增加而逐渐增大,当TiO2含量达到0.8wt%时,复合涂膜的拉伸强度最高,达到了12.3MPa,但当TiO2含量超过0.8wt%后,其拉伸强度反而随着TiO2含量的增加降低。其原因可能是:添加过多的纳米TiO2,容易在聚合物中发生团聚,从而导致复合材料形成力学缺陷,拉伸强度反而下降。
4)环氧树脂含量对复合涂膜的吸水率影响分析
实验发现,环氧树脂含量对复合涂膜的耐水性能会产生影响。
从图5可以看出,随着环氧树脂含量的增加,环氧树脂改性聚氨酯复合涂膜的吸水率从17.9%逐渐下降到4.2%。由此可知,环氧树脂的加入使聚氨酯交联度增大,涂膜的耐水性能增强。
5)复合涂膜的紫外吸收分析
复合涂膜的紫外吸收曲线图见图6,从下至上依次为环氧-聚氨酯、改性纳米TiO2/环氧-聚氨酯、纳米TiO2的紫外吸收曲线。
对比图6的紫外吸收曲线可知,改性纳米TiO2/环氧-聚氨酯在246nm~330nm处有较强的紫外吸收,相比于环氧-聚氨酯有更强的紫外吸收能力和更宽的吸收带,这种强而宽的紫外吸收是由纳米TiO2引起的。改性纳米TiO2/环氧-聚氨酯具有较强的紫外吸收能力,可使涂膜的表面产生强活性基团,从而使涂料具有抗紫外、抗老化的功能。
6)纳米TiO2含量对涂膜硬度及乳液稳定性能的影响分析
表1纳米TiO2含量对涂膜硬度及乳液稳定性能的影响
从表1可知,由于添加纳米TiO2增加了环氧-聚氨酯的交联度,使涂膜的硬度得到提高,但随着纳米TiO2含量增加,铅笔硬度和乳液的稳定性能反而减小,这可能与纳米TiO2的团聚现象有关。实验结果表明:当TiO2含量0.8wt%时,改性纳米TiO2/环氧-聚氨酯复合乳液在存放过程中不会出现沉淀且涂膜的铅笔硬度最高达3H。
综上所述,将油酸改性纳米TiO2表面的羟基与异氰酸酯基团、聚醚和环氧树脂(E51)发生逐步聚合反应,成功制得了性能优异的改性纳米TiO2/环氧-聚氨酯三元复合材料;
测试结果表明,改性纳米TiO2/环氧-聚氨酯涂膜稳定性能好,硬度高,耐水性能和力学性能强,抗紫外和抗老化性能亦有明显提高。
要说明的是,以上所述实施例是对本发明技术方案的说明而非限制,所属技术领域普通技术人员的等同替换或者根据现有技术而做的其他修改,只要没超出本发明技术方案的思路和范围,均应包含在本发明所要求的权利范围之内。
Claims (2)
1.一种改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法,其特征在于:包括如下步骤:
1)油酸改性纳米TiO2的制备:
将6~10g钛酸丁酯和0.8~1.2g油酸溶解于30~50mL的无水乙醇中,加入6~10g的Na2SO4·10H2O,磁力搅拌均匀,缓慢升温至60~70℃,氮气保护下反应1~3小时,得到淡黄色悬浊液;将淡黄色悬浊液进行抽滤、洗涤后得到沉淀,将所得沉淀溶解于30~50mL无水乙醇中,再抽滤、洗涤一次,最终将沉淀室温下真空干燥,即得油酸改性纳米TiO2,待用;
2)改性纳米TiO2/环氧树脂-聚氨酯三元复合材料的制备:
将步骤1)中制得的4~6g油酸改性纳米TiO2与30~50mL的丙酮均匀混合,调节pH值为7~8;将其分散液逐滴加入到5~8g的二苯基甲烷二异氰酸酯中,继续加入16~20mL聚醚和1~3滴二月桂酸二丁基锡,然后加入1~1.4mL一缩二乙二醇、10~15mL丙酮和3.4~3.8g二羟甲基丙酸,升温至70~80℃,反应2~3h;继续加入3~5g环氧树脂和2~4滴二月桂酸二丁基锡,50~70℃条件下反应1~3h;最后加入3.4~3.8mL三乙胺和40~60mL去离子水,磁力搅拌,乳化30~50min,脱去丙酮溶剂即得改性纳米TiO2/环氧树脂-聚氨酯三元复合材料。
2.一种如权利要求1所述的制备方法所制成的改性纳米TiO2/环氧-聚氨酯三元复合材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810666313.9A CN108774304A (zh) | 2018-06-26 | 2018-06-26 | 改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810666313.9A CN108774304A (zh) | 2018-06-26 | 2018-06-26 | 改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108774304A true CN108774304A (zh) | 2018-11-09 |
Family
ID=64026424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810666313.9A Pending CN108774304A (zh) | 2018-06-26 | 2018-06-26 | 改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108774304A (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110527064A (zh) * | 2019-08-21 | 2019-12-03 | 扬州工业职业技术学院 | 一种改性纳米TiO2聚氨酯复合乳液的制备方法 |
CN111072066A (zh) * | 2019-12-31 | 2020-04-28 | 扬州工业职业技术学院 | 一种油酸改性纳米TiO2的制备方法 |
CN111234507A (zh) * | 2020-03-23 | 2020-06-05 | 扬州工业职业技术学院 | 一种TiO2PU复合材料的制备方法 |
CN111777737A (zh) * | 2020-07-13 | 2020-10-16 | 江苏群创知识产权有限公司 | 一种纳米TiO2环氧-聚氨酯复合材料的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4843119A (en) * | 1987-01-22 | 1989-06-27 | Compagnie Francaise De Produits Industriels | Adhesive product for the bonding of steel, particularly in the automotive sheetwork operations |
US20060287463A1 (en) * | 2003-09-23 | 2006-12-21 | Jochen Wehner | Two-component composition for producing polyurethane gel coats for epoxy-resin and vinyl-esther resin composite materials |
CN101328383A (zh) * | 2008-07-17 | 2008-12-24 | 安徽大学 | 用于衬里手套水性聚氨酯涂层连接料的生产方法 |
CN101397400B (zh) * | 2007-09-30 | 2011-02-09 | 中橡集团曙光橡胶工业研究设计院 | 履带车辆负重轮纳米改性聚氨酯弹性体胎体材料及浇注工艺 |
CN102181218A (zh) * | 2011-03-18 | 2011-09-14 | 西北矿冶研究院 | 一种新型聚合物防腐涂层材料 |
CN106590395A (zh) * | 2016-11-29 | 2017-04-26 | 安徽圆梦建筑有限公司 | 一种耐腐蚀耐紫外线水性涂料 |
-
2018
- 2018-06-26 CN CN201810666313.9A patent/CN108774304A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4843119A (en) * | 1987-01-22 | 1989-06-27 | Compagnie Francaise De Produits Industriels | Adhesive product for the bonding of steel, particularly in the automotive sheetwork operations |
US20060287463A1 (en) * | 2003-09-23 | 2006-12-21 | Jochen Wehner | Two-component composition for producing polyurethane gel coats for epoxy-resin and vinyl-esther resin composite materials |
CN101397400B (zh) * | 2007-09-30 | 2011-02-09 | 中橡集团曙光橡胶工业研究设计院 | 履带车辆负重轮纳米改性聚氨酯弹性体胎体材料及浇注工艺 |
CN101328383A (zh) * | 2008-07-17 | 2008-12-24 | 安徽大学 | 用于衬里手套水性聚氨酯涂层连接料的生产方法 |
CN102181218A (zh) * | 2011-03-18 | 2011-09-14 | 西北矿冶研究院 | 一种新型聚合物防腐涂层材料 |
CN106590395A (zh) * | 2016-11-29 | 2017-04-26 | 安徽圆梦建筑有限公司 | 一种耐腐蚀耐紫外线水性涂料 |
Non-Patent Citations (6)
Title |
---|
CHEN YUFEI,等: "Characteristics and Properties of TiO2/EP-PU Composite", 《JOURNAL OF NANOMATERIALS》 * |
N. PIRHADY TAVANDASHTI,等: "Preparation and characterisation of silica/epoxy hybrid nanocomposite coatings containing boehmite nanoparticles for corrosion protection", 《CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY》 * |
刘新华,等: "聚氨酯改性纳米二氧化钛整理剂的制备和应用", 《印染》 * |
李坚,等: "纳米二氧化钦改性聚氨醋乳液性能初探", 《中国胶粘剂》 * |
艾九红: "纳米TiO2复合水性乳液涂料的制备", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
陈宇飞,等: "纳米二氧化钛表面化学改性及表征", 《哈尔滨师范大学自然科学学报》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110527064A (zh) * | 2019-08-21 | 2019-12-03 | 扬州工业职业技术学院 | 一种改性纳米TiO2聚氨酯复合乳液的制备方法 |
CN111072066A (zh) * | 2019-12-31 | 2020-04-28 | 扬州工业职业技术学院 | 一种油酸改性纳米TiO2的制备方法 |
CN111234507A (zh) * | 2020-03-23 | 2020-06-05 | 扬州工业职业技术学院 | 一种TiO2PU复合材料的制备方法 |
CN111777737A (zh) * | 2020-07-13 | 2020-10-16 | 江苏群创知识产权有限公司 | 一种纳米TiO2环氧-聚氨酯复合材料的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108774304A (zh) | 改性纳米TiO2/环氧-聚氨酯三元复合材料的制备方法 | |
DE60112656T2 (de) | Beschichtungszusammensetzung, Beschichtungsverfahren und beschichteter Gegenstand | |
EP1807457B1 (en) | Vinyl chloride resin composition and method for preparation thereof | |
EP2358822B1 (de) | Kratzfestbeschichtete polycarbonate mit hoher transparenz, verfahren zu deren herstellung und deren verwendung | |
CN111171607B (zh) | 一种制备亲水性炭黑的方法、亲水性炭黑及其应用 | |
EP3263651B1 (en) | Dispersion of titanium oxide particles in organic solvent, and production method for same | |
EP2275489A1 (en) | Alicyclic epoxy resin composition, cured product thereof, production method thereof, and rubbery polymer-containing resin composition | |
EP1549700B1 (de) | Schichtsystem und verfahren zu dessen herstellung | |
EP3263527B1 (en) | Method for producing organic solvent dispersion of titanium oxide particles | |
US20080176986A1 (en) | Zinc Oxide Nanoparticle Dispersions | |
CN110746794A (zh) | 一种超疏水性白炭黑的制备方法 | |
CN112457691B (zh) | 一种低光催化活性的消光剂及其制备方法和应用 | |
EP1726975A1 (en) | Method for producing plastic lens | |
CN100365076C (zh) | 原位接枝有机化合物的纳米炭黑及其制造方法 | |
CN108993413B (zh) | 一种氨基改性沉淀氧化硅的制备方法 | |
CN111393720A (zh) | 一种纳米氧化锌改性纳米晶纤维素增强天然橡胶及其制备方法 | |
CN112441593B (zh) | 表面疏水改性无水纳米硼酸锌的制备方法 | |
WO2012161191A1 (ja) | 表面変性された熱線遮蔽性微粒子の製造方法及びその方法により得られる熱線遮蔽性微粒子分散液 | |
CN112125312B (zh) | 二氧化硅纳米颗粒表面修饰氨基的方法 | |
CN1176162C (zh) | 水溶性接枝炭黑的制备方法 | |
EP4119617A1 (en) | Surface-coated inorganic particles, method for producing same, and organic-solvent dispersion of same | |
CN113272333B (zh) | 改性纤维素纤维粉末 | |
CN113461869A (zh) | 一种金属有机框架-碳酸钙复合晶体材料及其制备方法 | |
CN116606469B (zh) | 一种力学性能强的阻燃膜材料及其制备方法 | |
CN116640505B (zh) | 一种功能性可光固化皮革涂饰剂体系及其制备方法和应用 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181109 |