乳液复合高强聚丙烯酰胺水凝胶的制备及表征
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摘要
凝胶作为一种软材料,主要通过人工合成或自然环境中得到,在生物医用及工农业中有着广泛的应用。由于凝胶含有大量水分,通常被认为强度很低。但是动物软骨、肌肉等天然凝胶具有接近橡胶的高强度,使人们重新考虑其力学性能与其结构的关系。因此,探索凝胶强度与其内部结构的关系成为当前国内外一个十分重要的研究热点。
虽然最近几年高强凝胶如双网络结构凝胶,有机-无机复合凝胶,大分子微球复合凝胶等取得极大的进展,但是其制备过程耗费时间长,或者凝胶性能受到其内部结构缺陷等影响,制备方式方法还需进一步的改进及创新。本文通过设计两种稳定的未聚合乳液组成的交联剂体系,与丙烯酰胺共聚首次制备了一系列乳液复合高强凝胶,并且重点讨论了凝胶力学性能与乳液尺寸及浓度的关系。主要内容如下：
1.通过纳米二氧化硅与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(TPM)自发形成的乳液,然后与丙烯酰胺单体共聚制备高强凝胶。经过改变纳米SiO2与TPM的比例,制备不同尺寸的乳液颗粒,然后在不同条件下观察乳液的稳定性,并考察制备凝胶各组分对乳液稳定性的影响；通过不同浓度和不同尺寸的乳液与丙烯酰胺单体共聚,制备不同机械性能的高强凝胶。凝胶断裂伸长率在373～757%,拉伸强度在70～148kPa,凝胶可被压缩至80%,压缩强度可在10MPa以上,远远超过小分子交联的聚丙烯酰胺凝胶。
2.通过纳米四氧化三铁与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(TPM)自发形成的乳液颗粒,与丙烯酰胺单体共聚制备具有磁性的高强凝胶。动态光散射测试表明,乳液颗粒尺寸与两者比例存在密切关系,并考察凝胶中各组分对乳液稳定性的影响；通过不同浓度和不同尺寸的乳液与丙烯酰胺单体共聚,制备了断裂伸长率在301～548%,拉伸强度在140kPa以上,凝胶可被压缩至80%,压缩强度可在15MPa以上。整体力学性能与SiO2/TPM相比有着极大的提升,这主要归因于Fe3O4/TPM乳液体系粒径更小分布更单一,有效交联密度更大。
As a soft material, hydrogels has broad application on the biomedical industry and agriculture, which mainly come from artificial synthetic or natural environment. The strength of hydrogel is usually thought to be low because of large amount of water within it. But strength of natural hydrogels such as animal cartilage, muscle are very high near rubber, to make people reconsider relationship between hydrogel strength and internal structure. Therefore, to explore the relationship between internal structure and hydrogel strength, it is a very important research issue at current home and abroad.
Material scientists had made great progress on high-strength hydrogel in recent years, such as double-network gel, organic-inorganic nano composite hydrogel, macromolecular microspheres composite hydrogels. But the synthesis process takes a long time, or performance of hydrogel is seriously affected by the defects of the internal structure. The approach of synthesis and the ways to high -strength gel need to be further improvement and innovation. The main purpose of this research is to prepare high -strength gel by designing of a specific cross-linking agent system. The main idea as follows:preparing un-polymeric emulsion through two different tactics, and hydrogel prepared by latex copolymerize with monomer acrylamide.
1.The high strength hydrogel is prepared by copolymerizing monomer acrylamide and latex; latex comes from emulsions formed spontaneously by nano-silica and y-methacryloxypropyltrimethoxysilane (TPM); and the formation different sizes of emulsion varies with the ratio of nano-SiO2 to TPM. The emulsion stability was then observed under different conditions, and we discuss the function of different components to the pre-gel emulsion stability. High-strength gel was prepared by different concentrations and different sizes of latex with acrylamide monomer, stretching between 373～757%, the tensile strength between 70～148kPa; gel can be compressed to 80%, and compressive strength can be more than 10MPa. All above hydrogel's strength is far more than common chemical polymer hydrogel.
2. The magnetic high-strength hydrogel is prepared by copolymerizing monomer acrylamide and latex; latex comes from emulsions formed spontaneously by magnetite nanoparticles and y-methacryloxypropyltrimethoxysilane(TPM). Dynamic light scattering tests showed that the emulsion particle size was within 100nm in this research, and there is close relationship between size and the ratio of TPM to Fe3O4 nanoparticles. We discuss the function of different components to the pre-gel emulsion stability. High-strength gel was prepared by different concentrations and different sizes of latex with acrylamide monomer under mild conditions. The gels can be stretching in the range of 300 to 548%, tensile strength more than 140kPa; the gels can be compressed to 80%, and compressive more than 15MPa. Compared to SiO2/TPM/AM composite gels, the overall mechanical properties have greatly improved, mainly due to more effective crosslinking density.
虽然最近几年高强凝胶如双网络结构凝胶,有机-无机复合凝胶,大分子微球复合凝胶等取得极大的进展,但是其制备过程耗费时间长,或者凝胶性能受到其内部结构缺陷等影响,制备方式方法还需进一步的改进及创新。本文通过设计两种稳定的未聚合乳液组成的交联剂体系,与丙烯酰胺共聚首次制备了一系列乳液复合高强凝胶,并且重点讨论了凝胶力学性能与乳液尺寸及浓度的关系。主要内容如下：
1.通过纳米二氧化硅与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(TPM)自发形成的乳液,然后与丙烯酰胺单体共聚制备高强凝胶。经过改变纳米SiO2与TPM的比例,制备不同尺寸的乳液颗粒,然后在不同条件下观察乳液的稳定性,并考察制备凝胶各组分对乳液稳定性的影响；通过不同浓度和不同尺寸的乳液与丙烯酰胺单体共聚,制备不同机械性能的高强凝胶。凝胶断裂伸长率在373～757%,拉伸强度在70～148kPa,凝胶可被压缩至80%,压缩强度可在10MPa以上,远远超过小分子交联的聚丙烯酰胺凝胶。
2.通过纳米四氧化三铁与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(TPM)自发形成的乳液颗粒,与丙烯酰胺单体共聚制备具有磁性的高强凝胶。动态光散射测试表明,乳液颗粒尺寸与两者比例存在密切关系,并考察凝胶中各组分对乳液稳定性的影响；通过不同浓度和不同尺寸的乳液与丙烯酰胺单体共聚,制备了断裂伸长率在301～548%,拉伸强度在140kPa以上,凝胶可被压缩至80%,压缩强度可在15MPa以上。整体力学性能与SiO2/TPM相比有着极大的提升,这主要归因于Fe3O4/TPM乳液体系粒径更小分布更单一,有效交联密度更大。
As a soft material, hydrogels has broad application on the biomedical industry and agriculture, which mainly come from artificial synthetic or natural environment. The strength of hydrogel is usually thought to be low because of large amount of water within it. But strength of natural hydrogels such as animal cartilage, muscle are very high near rubber, to make people reconsider relationship between hydrogel strength and internal structure. Therefore, to explore the relationship between internal structure and hydrogel strength, it is a very important research issue at current home and abroad.
Material scientists had made great progress on high-strength hydrogel in recent years, such as double-network gel, organic-inorganic nano composite hydrogel, macromolecular microspheres composite hydrogels. But the synthesis process takes a long time, or performance of hydrogel is seriously affected by the defects of the internal structure. The approach of synthesis and the ways to high -strength gel need to be further improvement and innovation. The main purpose of this research is to prepare high -strength gel by designing of a specific cross-linking agent system. The main idea as follows:preparing un-polymeric emulsion through two different tactics, and hydrogel prepared by latex copolymerize with monomer acrylamide.
1.The high strength hydrogel is prepared by copolymerizing monomer acrylamide and latex; latex comes from emulsions formed spontaneously by nano-silica and y-methacryloxypropyltrimethoxysilane (TPM); and the formation different sizes of emulsion varies with the ratio of nano-SiO2 to TPM. The emulsion stability was then observed under different conditions, and we discuss the function of different components to the pre-gel emulsion stability. High-strength gel was prepared by different concentrations and different sizes of latex with acrylamide monomer, stretching between 373～757%, the tensile strength between 70～148kPa; gel can be compressed to 80%, and compressive strength can be more than 10MPa. All above hydrogel's strength is far more than common chemical polymer hydrogel.
2. The magnetic high-strength hydrogel is prepared by copolymerizing monomer acrylamide and latex; latex comes from emulsions formed spontaneously by magnetite nanoparticles and y-methacryloxypropyltrimethoxysilane(TPM). Dynamic light scattering tests showed that the emulsion particle size was within 100nm in this research, and there is close relationship between size and the ratio of TPM to Fe3O4 nanoparticles. We discuss the function of different components to the pre-gel emulsion stability. High-strength gel was prepared by different concentrations and different sizes of latex with acrylamide monomer under mild conditions. The gels can be stretching in the range of 300 to 548%, tensile strength more than 140kPa; the gels can be compressed to 80%, and compressive more than 15MPa. Compared to SiO2/TPM/AM composite gels, the overall mechanical properties have greatly improved, mainly due to more effective crosslinking density.
引文
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