WO2012055075A1 - Heat-resistant composite antibacterial functional material and preparation method thereof - Google Patents
Heat-resistant composite antibacterial functional material and preparation method thereof Download PDFInfo
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- WO2012055075A1 WO2012055075A1 PCT/CN2010/001860 CN2010001860W WO2012055075A1 WO 2012055075 A1 WO2012055075 A1 WO 2012055075A1 CN 2010001860 W CN2010001860 W CN 2010001860W WO 2012055075 A1 WO2012055075 A1 WO 2012055075A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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Definitions
- the invention relates to an antibacterial functional material and a preparation method thereof, in particular to a novel heat-resistant composite antibacterial functional material and a preparation method thereof by using an ionic liquid and an inorganic carrier as raw materials.
- the heat-resistant composite antibacterial functional material is a hotspot in the research of antibacterial materials.
- This kind of composite material not only has the characteristics of high temperature resistance of inorganic materials, but also has antibacterial effect of organic antibacterial materials, good sterilization effect and fast sterilization speed. advantage.
- Organic antibacterial materials such as chlorhexidine acetate have been successfully added to inorganic layered carrier materials such as hydrotalcite and montmorillonite, but these composite antibacterial materials have a temperature tolerance of less than 200 °C, and some processes that need to withstand high temperatures Medium (such as plastics, resins, etc.), it is difficult to reach the lower temperature limit required by the process. This means that the application of this material is limited.
- Reference 1 D, Yang.; P.
- the object of the present invention is to: improve the heat resistance of the organic antibacterial material by fully utilizing the broad-spectrum antibacterial property of the organic antibacterial material; thereby providing an intercalation assembly of the ionic liquid having good antibacterial property and the a-pure acid ammonia titanium. , synthetic heat-resistant composite antibacterial functional materials.
- the material has an antibacterial efficiency of more than 90% against sensitive bacteria, and has a structure and antibacterial property which can be maintained at a temperature of 250 ° C or higher.
- Another object of the present invention is to provide a process for producing a heat-resistant composite antibacterial material which is advantageous for large-scale industrial production, has low synthesis cost, simple process, and high purity and high yield of the synthesized product.
- the invention provides a heat-resistant composite antibacterial functional material, which is characterized in that: the ionic liquid and the ⁇ -pure acid ammonia titanium are intercalated and assembled to obtain a heat-resistant composite antibacterial function.
- the chemical formula of the heat-resistant composite antibacterial functional material is as follows:
- A represents a cation of an ionic liquid, and b is 1 or 2;
- the ionic liquid is: an imidazole ionic liquid.
- the inorganic carrier material is a-titanium titanium (the molecular structural formula is ⁇ ( ⁇ 4 ⁇ 0 4 ) 2 ⁇ 2 0), and the synthesis process thereof is: ⁇ -pity hydrogen titanium and 1 according to a molar ratio of ammonia: 10 ⁇ 10: 1 mixture, synthesized using conventional synthesis process, the [eta] a- pity bicarbonate titanium lamina - ⁇ group substituted ⁇ 4 + + is obtained ⁇ - amino acid pity titanium.
- the preparation method of the heat-resistant composite antibacterial functional material provided by the invention comprises the following steps:
- the ionic liquid is: an imidazole ionic liquid
- step 2) The ionic liquid weighed in step 1) and the a-p-acid titanium hydride are placed in a solvent at a temperature of 20 ° C to 90 ° C under normal pressure, according to the total amount of ionic liquid and inorganic carrier material and the mass of the solvent.
- the Ti(A) b (P0 4 ) 2 composite antibacterial material solution obtained in the step 2) is centrifuged, washed thoroughly with water and ethanol, and dried under vacuum at normal temperature and pressure to obtain Ti(A) b (P0).
- 2 powder intercalated ionic liquid ⁇ - Rei ammonium antibacterial titanium composite material wherein the cation of the ionic liquid wherein the representative ⁇ , b is 1 or 2.
- Ti(NH 4 P0 4 ) 2 .H 2 0) is synthesized by mixing ⁇ -digestive hydrogen titanium with ammonia water in a molar ratio of 1:10 to 10:1, and synthesizing by a conventional synthesis process, a-poic acid titanium layer ⁇ on plate - ⁇ group ⁇ 4 + + is obtained a- substituted amino acid pity titanium.
- the ratio of the ionic liquid to the a-pure acid ammonia titanium compounding ratio preferably the molar ratio of the ionic liquid to the ⁇ -petic acid ammonia titanium is 1: 1 to 1: 2 .
- the solvent is a mixture of water and ethanol, and the water The volume ratio is 10 to 90%; the proportion of ethanol is 10 to 90%.
- the heat-resistant composite antibacterial functional material provided by the preparation method of the invention has an antibacterial rate of more than 90% against the antibacterial susceptible bacteria.
- the antibacterial-sensitive bacteria are gram-positive bacteria and gram-negative bacteria. Mainly including Escherichia coli, Staphylococcus aureus
- the heat-resistant composite antibacterial functional material of the present invention is superior to the existing antibacterial material in that:
- the heat-resistant composite antibacterial functional material of the present invention allows the ionic liquid to enter the ⁇ - by ion-exchange reaction of the cationic group of the ionic liquid with -NH 4+ on the a-p-acid-titanium-titanium plate-OH plate.
- the interlayer of the acid-ammonia titanium alloy is tightly bonded to -0 on the laminate, and the formed ionic liquid intercalates the product of ⁇ -diuretic ammonia titanium.
- the product of the ionic liquid intercalation a-titanium titanium is detected by XRD (X-ray diffraction) and FTIR (infrared spectroscopy).
- the experimental results show that the ionic liquid has been successfully embedded in the interlayer of ⁇ -pity zirconate
- TG-FTIR Hot-heavy-infrared combined
- the synthetic heat-resistant composite antibacterial functional material has high heat resistance; it can maintain the structure and antibacterial properties at a temperature of 250 ° C and above.
- the material has spectral antibacterial, environmental friendliness, good thermal stability and good sustained release effect.
- the antibacterial efficiency against sensitive bacteria is over 90%.
- the product is inexpensive, has controllability to the amount of ionic liquid used, and is an environmentally friendly antibacterial material.
- the method for preparing the heat-resistant composite antibacterial functional material solves the problems existing in the prior art from two aspects: (1) using an imidazole-based ionic liquid as an antibacterial component (imidazole-based ionic liquid means one type of containing The general name of the ionic liquid of the imidazole group), domestic and foreign studies have shown that the imidazole organic substance exhibits good antibacterial properties, and the decomposition temperature is generally above 300 ° C, and has good heat resistance. (2) a-diuretic ammonia titanium as an inorganic carrier.
- the ⁇ -pure acid ammonia titanium used in the present invention is a layered compound having good cation exchange ability obtained by intercalating and assembling a-distilled acid hydrogen titanium and ammonia water, which has a large interlayer spacing and is easy to be combined with. Organic matter is intercalated. This method is advantageous for large-scale industrial production.
- Figure 1 is a view showing the structure of the ionic liquid intercalation layer a-diuretic ammonia titanium of the present invention
- the present invention utilizes the preparation method of the present invention to prepare an imidazolium ionic liquid intercalation alpha-pure acid ammonium titanium composite antibacterial material having the following formula: Ti[(C n MIM)P0 4 ] 2 ;
- C n MIM 1-mercapto-3-methylimidazolium cation (n is a natural number of 1 to 20), and the specific preparation steps of the material are as follows:
- the ionic liquid described in this embodiment is: an imidazole ionic liquid.
- the conventional synthetic process of imidazolium ionic liquid can be carried out by a person skilled in the art, for example, by a combination of a mercapto imidazolium cation and an F-, Cl-, Br-, I-anion, according to a conventional process to obtain a halogenated mercapto imidazolium ionic liquid;
- the inorganic carrier material is ⁇ -pure acid ammonia titanium (the molecular structural formula is ⁇ ( ⁇ 4 ⁇ 0 4 ) 2 ⁇ 2 0), and the synthesis process thereof is: ⁇ -pity hydrogen titanium and ammonia water in a molar ratio of 1:10 ⁇ 10: 1 mixing, a-pure acid hydrogen titanium laminate - ⁇ on the fluorene group + ⁇ 4 + substitution to obtain a-diuretic ammonia titanium, using a synthetic process well known to those skilled in the art.
- step 2) mixing the 1-tetradecyl-3-methylimidazolium ionic liquid weighed in step 1) with ⁇ -petic acid ammonia titanium in a solvent having a temperature of 20 ° C under normal pressure, wherein, mixing The ratio is the ratio of the total amount of the 1-tetradecyl-3-methylimidazolium ionic liquid of the bromide and the a-titanium titanium bromide 1:1, and the mass ratio of the solvent is 1:1, and the reaction is stirred for 72 hours.
- the liquid 1-tetradecyl-3methylimidazolium cation undergoes an ion exchange reaction with H + on the ⁇ - p-acid ammonium titanium plate-OH to allow the ionic liquid to enter the interlayer of the ⁇ - p-acid ammonium titanium.
- the structure of ⁇ -pure acid ammonia titanium is shown in Figure 1;
- the 1-tetradecyl-3 methylimidazolium ionic liquid obtained by the step 2) is intercalated into the ⁇ -pure acid ammonia titanium organic-inorganic composite antibacterial material solution, and is thoroughly washed with water and ethanol (using conventional The process is carried out by drying at normal temperature and normal pressure to obtain a composite antibacterial functional material of a white powdery 1-tetradecyl-3-methylimidazolium ionic liquid intercalation layer a-diuretic ammonia titanium.
- the structure of the ionic liquid intercalation a-pure ammonia titanium is shown in Figure 1.
- the antibacterial effect of the composite antibacterial functional material is shown in Table 2.
- the solvent used in this embodiment is 10% of the total volume of water; ethanol accounts for the total volume
- a 1-hexyl-3-methylimidazolium ionic liquid can also be used, and according to the above reaction step, a 1-octyl-3-methylimidazolium ionic liquid intercalation layer ⁇ -o-acid ammonium salt can be obtained.
- Titanium composite antibacterial material can also be used, and according to the above reaction step, a 1-octyl-3-methylimidazolium ionic liquid intercalation layer ⁇ -o-acid ammonium salt.
- the 1-octadecyl-3-methylimidazolium ionic liquid can also be used, and according to the above reaction step, the 1-octadecyl-3-methylimidazolium ionic liquid intercalation layer ⁇ -pity is obtained.
- Ammonium ammonium phosphate composite antibacterial material can also be used, and according to the above reaction step, the 1-octadecyl-3-methylimidazolium ionic liquid intercalation layer ⁇ -pity is obtained.
- Ammonium ammonium phosphate composite antibacterial material can also be used, and according to the above reaction step, the 1-octadecyl-3-methylimidazolium ionic liquid intercalation layer ⁇ -pity is obtained.
- the antibacterial activity of the composite was tested by the inhibition loop test method.
- the evaluation method is as follows: The diameter of the inhibition zone is greater than 7 mm, which is judged to have a bacteriostatic effect; the diameter of the inhibition zone is less than or equal to 7 mm, and is judged to have no bacteriostatic effect.
- the solvent in the second embodiment may be a mixture of water and ethanol, the volume ratio of water is 90%; the proportion of ethanol is 10%, or the proportion of water is 95%; the proportion of ethanol is 5% and the like are all possible, which is also competent to those skilled in the art.
Abstract
Heat-resistant composite antibacterial functional material and the preparation method thereof are provided. Imidazole ionic liquid and Ti ammonium α-phosphate undergo intercalation assembling to prepare the antibacterial materials. The general formula of the antibacterial material is shown as follows: Ti(A)b(PO4)2, wherein A represents the cation of imidazole ionic liquid, b represents 1 or 2. The antibacterial material can keep its structure and antibacterial function unchanged under the temperature of 250℃ or above, and have more than 90% antibacterial efficiency for sensitive bacteria.
Description
一种耐热型复合抗菌功能材料及其制备方法 Heat-resistant composite antibacterial functional material and preparation method thereof
技术领域 Technical field
本发明涉及一种抗菌功能材料及其制备方法，特别是涉及一种以 离子液体和无机载体为原料，合成一种新型耐热型复合抗菌功能材料 及其制备方法。 背景技术 The invention relates to an antibacterial functional material and a preparation method thereof, in particular to a novel heat-resistant composite antibacterial functional material and a preparation method thereof by using an ionic liquid and an inorganic carrier as raw materials. Background technique
耐热型复合抗菌功能材料是目前抗菌材料研究的热点领域，这种 材料既具有这种复合材料既具有无机材料耐高温的特性，又具有有机 抗菌材料光谱抗菌， 杀菌效果好， 杀菌速度快的优点。 醋酸洗必泰等 有机抗菌材料已经被成功加入到无机层状载体材料如水滑石、蒙脱土 之中， 但是这些复合抗菌材料的耐受温度不到 200 °C， 在一些需要耐 受高温的工艺中 （如塑料、 树脂等工艺）， 还难以达到工艺所要求的 温度下限。 也就是说该材料的应用受到限制。 例如： 参考文献 1 (D, Yang.; P. Yuan.; J. X. Zhu.; H. -P. He., Synthesisi and charzcterization of antibacterial compounds suing montmorillonite and chlorhexidine acetate. J. Therm. Anal. Calorim. 2007, 89(3), 847-852 ) 所介绍的。 发明内容 The heat-resistant composite antibacterial functional material is a hotspot in the research of antibacterial materials. This kind of composite material not only has the characteristics of high temperature resistance of inorganic materials, but also has antibacterial effect of organic antibacterial materials, good sterilization effect and fast sterilization speed. advantage. Organic antibacterial materials such as chlorhexidine acetate have been successfully added to inorganic layered carrier materials such as hydrotalcite and montmorillonite, but these composite antibacterial materials have a temperature tolerance of less than 200 °C, and some processes that need to withstand high temperatures Medium (such as plastics, resins, etc.), it is difficult to reach the lower temperature limit required by the process. This means that the application of this material is limited. For example: Reference 1 (D, Yang.; P. Yuan.; JX Zhu.; H. -P. He., Synthesisi and charzcterization of antibacterial compounds suing montmorillonite and chlorhexidine acetate. J. Therm. Anal. Calorim. 2007, 89(3), 847-852) introduced. Summary of the invention
本发明的目的在于： 为了充分利用有机抗菌材料的广谱抗菌性 能， 提高有机抗菌材料的耐热性能； 从而提供一种将具有良好抗菌性 能的离子液体与 a-憐酸氨钛进行插层组装，合成耐热型复合抗菌功能 材料。 该材料对敏感菌的抗菌效率在 90%以上， 具有能在 250°C及以 上的温度保持结构和抗菌性能不变。 The object of the present invention is to: improve the heat resistance of the organic antibacterial material by fully utilizing the broad-spectrum antibacterial property of the organic antibacterial material; thereby providing an intercalation assembly of the ionic liquid having good antibacterial property and the a-pure acid ammonia titanium. , synthetic heat-resistant composite antibacterial functional materials. The material has an antibacterial efficiency of more than 90% against sensitive bacteria, and has a structure and antibacterial property which can be maintained at a temperature of 250 ° C or higher.
本发明的另一目的提供一种制备耐热型复合抗菌材料的方法，该 制备方法有利于大规模工业生产， 合成成本低、 工艺简单， 而且所合 成的产品纯度高， 产率高。 Another object of the present invention is to provide a process for producing a heat-resistant composite antibacterial material which is advantageous for large-scale industrial production, has low synthesis cost, simple process, and high purity and high yield of the synthesized product.
本发明的目的是这样实现的： The object of the invention is achieved in this way:
本发明提供的一种耐热型复合抗菌功能材料， 其特征在于： 其为 离子液体与 α-憐酸氨钛进行插层组装合成得到耐热型复合抗菌功能
材料， 所述的耐热型复合抗菌功能材料的化学通式如下： The invention provides a heat-resistant composite antibacterial functional material, which is characterized in that: the ionic liquid and the α-pure acid ammonia titanium are intercalated and assembled to obtain a heat-resistant composite antibacterial function. The chemical formula of the heat-resistant composite antibacterial functional material is as follows:
Ti(A)b(P04)2; Ti(A) b (P0 4 ) 2;
其中， 式中 A代表离子液体的阳离子, b为 1或 2; Wherein A represents a cation of an ionic liquid, and b is 1 or 2;
所述的离子液体为： 咪唑离子液体。 The ionic liquid is: an imidazole ionic liquid.
在上述的技术方案中，所述的无机载体材料为 a-憐酸氨钛（分子 结构式为 Τί(ΝΗ4Ρ04)2·Η20)， 其合成过程为： α-憐酸氢钛与氨水按照 摩尔比 1:10〜10: 1混合， 采用常规合成工艺进行合成， a-憐酸氢钛层 板 -ΟΗ基团上的 Η+被 ΝΗ4 +取代而得到 α-憐酸氨钛。 In the above technical solution, the inorganic carrier material is a-titanium titanium (the molecular structural formula is Τί(ΝΗ 4 Ρ0 4 ) 2 ·Η 2 0), and the synthesis process thereof is: α-pity hydrogen titanium and 1 according to a molar ratio of ammonia: 10~10: 1 mixture, synthesized using conventional synthesis process, the [eta] a- pity bicarbonate titanium lamina -ΟΗ group substituted ΝΗ 4 + + is obtained α- amino acid pity titanium.
本发明提供的耐热型复合抗菌功能材料的制备方法：包括以下步 骤： The preparation method of the heat-resistant composite antibacterial functional material provided by the invention comprises the following steps:
1 )按照离子液体与 α-憐酸氨钛的原料摩尔比为 1 : 10〜10 : 1的比 例配料； 1) according to the ratio of the molar ratio of the ionic liquid to the raw material of the α-pure acid ammonia titanium is 1:10~10:1;
其中， 所述的离子液体为： 咪唑离子液体； Wherein, the ionic liquid is: an imidazole ionic liquid;
2 ) 在常压下将步骤 1 ) 称取的离子液体和 a-憐酸氢钛放入温度 为 20°C〜90°C的溶剂中， 按离子液体和无机载体材料总量与溶剂的 质量比为 1 :1〜1: 1000的比例混合搅拌， 进行合成反应 2小时〜 72小 时； 离子液体的阳离子基团与 α -憐酸铵钛层板 -0H上的 H+发生离子 交换反应， 使离子液体得以进入到 α -憐酸铵钛的层间， 与层板上的 -0—紧密结合， 合成了离子液体插层 α -憐酸铵钛的 Ti(A)b(P04)2复合 抗菌材料溶液； 2) The ionic liquid weighed in step 1) and the a-p-acid titanium hydride are placed in a solvent at a temperature of 20 ° C to 90 ° C under normal pressure, according to the total amount of ionic liquid and inorganic carrier material and the mass of the solvent. Mixing and stirring at a ratio of 1:1 to 1:1000, and performing a synthesis reaction for 2 hours to 72 hours; the cationic group of the ionic liquid undergoes an ion exchange reaction with H + on the α-pity ammonium titanium plate-0H, so that The ionic liquid can enter the interlayer of α-pure ammonium titanium and closely combine with -0 on the laminate to synthesize Ti(A) b (P0 4 ) 2 composite of ionic liquid intercalation α-pure ammonium. Antibacterial material solution;
3 ) 然后将步骤 2 )得到的 Ti(A)b(P04)2复合抗菌材料溶液， 进行 离心分离， 再用水和乙醇充分洗涤， 经常温常压真空干燥， 得到 Ti(A)b(P04)2的粉末状的离子液体插层 α -憐酸铵钛复合抗菌材料；其 中， 式中 Α代表离子液体的阳离子, b为 1或 2。 3) Then, the Ti(A) b (P0 4 ) 2 composite antibacterial material solution obtained in the step 2) is centrifuged, washed thoroughly with water and ethanol, and dried under vacuum at normal temperature and pressure to obtain Ti(A) b (P0). 4) 2 powder intercalated ionic liquid α - Rei ammonium antibacterial titanium composite material; wherein the cation of the ionic liquid wherein the representative Α, b is 1 or 2.
在上述的技术方案中， 所述的 a-憐酸氨钛 （分子结构式为 In the above technical solution, the a-diuretic ammonia titanium (the molecular structural formula is
Ti(NH4P04)2.H20)由：α-憐酸氢钛与氨水按照摩尔比 1:10〜： 10:1混合， 采用常规合成工艺进行合成， a-憐酸氢钛层板 -ΟΗ基团上的 Η+被 ΝΗ4 +取代而得到 a-憐酸氨钛。 Ti(NH 4 P0 4 ) 2 .H 2 0) is synthesized by mixing α-digestive hydrogen titanium with ammonia water in a molar ratio of 1:10 to 10:1, and synthesizing by a conventional synthesis process, a-poic acid titanium layer Η on plate -ΟΗ group ΝΗ 4 + + is obtained a- substituted amino acid pity titanium.
在上述的技术方案中， 所述的离子液体与 a-憐酸氨钛配料比例， 优选离子液体与 α-憐酸氨钛的摩尔比为 1 : 1〜1 : 2。 In the above technical solution, the ratio of the ionic liquid to the a-pure acid ammonia titanium compounding ratio, preferably the molar ratio of the ionic liquid to the α-petic acid ammonia titanium is 1: 1 to 1: 2 .
在上述的技术方案中， 所述的溶剂为水和乙醇混合物， 水所占的
体积比例为 10〜90%； 乙醇所占的比例为 10〜90%。 In the above technical solution, the solvent is a mixture of water and ethanol, and the water The volume ratio is 10 to 90%; the proportion of ethanol is 10 to 90%.
本发明的制备方法提供的耐热型复合抗菌功能材料对抗菌敏感 菌的抗菌率在 90%以上。 所述的抗菌敏感菌种为革兰氏阳性菌 (gram-positive bacteria)禾口革兰氏阴性菌 (gram-negative bacteria)。主要 包括大肠埃希式菌属 (Escherichia coli)、 金色葡萄球菌属 The heat-resistant composite antibacterial functional material provided by the preparation method of the invention has an antibacterial rate of more than 90% against the antibacterial susceptible bacteria. The antibacterial-sensitive bacteria are gram-positive bacteria and gram-negative bacteria. Mainly including Escherichia coli, Staphylococcus aureus
(Staphylococcus aureus) 链霉菌属 (Streptomyces)、 链球菌属 (Staphylococcus aureus) Streptomyces, Streptococcus
(Streptococcus)禾口嗜月巿军团菌 (legionella pneumophila)。 (Streptococcus) and Legionella pneumophila.
本发明的耐热型复合抗菌功能材料与现有的抗菌材料相比，其优 点在于： The heat-resistant composite antibacterial functional material of the present invention is superior to the existing antibacterial material in that:
由于本发明的耐热型复合抗菌功能材料是通过将离子液体的阳 离子基团与 a-憐酸氨钛层板 -OH上的 -NH4+发生离子交换反应， 使离 子液体得以进入到 α-憐酸氨钛的层间， 与层板上的 -0—紧密结合， 所 形成的离子液体插层 α-憐酸氨钛的产物。 该离子液体插层 a-憐酸氨 钛的产物经 XRD(X射线衍射)和 FTIR (红外光谱)检测，实验结果表明 离子液体已经成功地嵌入到 α-憐酸锆的层间， TG-FTIR (热重-红外联 用)实验证实了 a-憐酸锆的存在提高了离子液体的热反应温度， 并且 α-憐酸锆层板和离子液体之间具有很强的主客体效应， 使得所合成的 耐热型复合抗菌功能材料具有很高的耐热性； 能在 250°C及以上的温 度保持结构和抗菌性能不变。 The heat-resistant composite antibacterial functional material of the present invention allows the ionic liquid to enter the α- by ion-exchange reaction of the cationic group of the ionic liquid with -NH 4+ on the a-p-acid-titanium-titanium plate-OH plate. The interlayer of the acid-ammonia titanium alloy is tightly bonded to -0 on the laminate, and the formed ionic liquid intercalates the product of α-diuretic ammonia titanium. The product of the ionic liquid intercalation a-titanium titanium is detected by XRD (X-ray diffraction) and FTIR (infrared spectroscopy). The experimental results show that the ionic liquid has been successfully embedded in the interlayer of α-pity zirconate, TG-FTIR (Hot-heavy-infrared combined) experiments confirmed that the presence of a-zirconium zirconate increases the thermal reaction temperature of the ionic liquid, and has a strong host-guest effect between the α-pity zirconium laminate and the ionic liquid. The synthetic heat-resistant composite antibacterial functional material has high heat resistance; it can maintain the structure and antibacterial properties at a temperature of 250 ° C and above.
该材料具有光谱抗菌、 环境友好、 热稳定性好和缓释效果好。对 敏感菌的抗菌效率在 90%以上。 The material has spectral antibacterial, environmental friendliness, good thermal stability and good sustained release effect. The antibacterial efficiency against sensitive bacteria is over 90%.
其次， 产品价格低廉， 对所离子液体的用量具有可控性， 是一种 环境友好的抗菌材料。 Secondly, the product is inexpensive, has controllability to the amount of ionic liquid used, and is an environmentally friendly antibacterial material.
本发明提供的制备耐热型复合抗菌功能材料的方法，从两个方面 解决了已有技术存在的问题：（1 )将咪唑类离子液体作为抗菌组分（咪 唑类离子液体是指一类含有咪唑基团的离子液体的总称）， 国内外研 究表明， 咪唑类有机物表现出良好的抗菌性能， 同时分解温度一般都 在 300°C以上， 具有良好的耐热性。 （2) a-憐酸氨钛作为无机载体。 本发明中所使用的 α-憐酸氨钛是 a-憐酸氢钛与氨水进行插层组装后 得到的一种具有良好阳离子交换能力的层状化合物，它具有较大的层 间距， 易于与有机物进行插层组装。 该方法有利于大规模工业生产。
附图说明 The method for preparing the heat-resistant composite antibacterial functional material provided by the invention solves the problems existing in the prior art from two aspects: (1) using an imidazole-based ionic liquid as an antibacterial component (imidazole-based ionic liquid means one type of containing The general name of the ionic liquid of the imidazole group), domestic and foreign studies have shown that the imidazole organic substance exhibits good antibacterial properties, and the decomposition temperature is generally above 300 ° C, and has good heat resistance. (2) a-diuretic ammonia titanium as an inorganic carrier. The α-pure acid ammonia titanium used in the present invention is a layered compound having good cation exchange ability obtained by intercalating and assembling a-distilled acid hydrogen titanium and ammonia water, which has a large interlayer spacing and is easy to be combined with. Organic matter is intercalated. This method is advantageous for large-scale industrial production. DRAWINGS
图 1是本发明离子液体插层 a-憐酸氨钛的结构; Figure 1 is a view showing the structure of the ionic liquid intercalation layer a-diuretic ammonia titanium of the present invention;
图面说明如下： α-磷酸氨钛的层板 The drawing is as follows: Layer of α-ammonia titanium phosphate
ONH4 + ONH4 + ONH4 + ONH 4 + ONH 4 + ONH 4 +
/wwwwww ^) 离子液体的阳离子 具体实舫式 /wwwwww ^) cations of ionic liquids
下面结合具体实施例对本发明作进一步说明，但本发明要求保护 的范围并不局限于实施例所表达的范围。 The invention is further illustrated by the following specific examples, but the scope of the invention is not limited to the scope of the embodiments.
实施例 1 Example 1
本实施例利用本发明的制备方法， 来制备的咪唑离子液体插层 α -憐酸铵钛复合抗菌材料， 具有如下通式： Ti[(CnMIM)P04]2; 其中，The present invention utilizes the preparation method of the present invention to prepare an imidazolium ionic liquid intercalation alpha-pure acid ammonium titanium composite antibacterial material having the following formula: Ti[(C n MIM)P0 4 ] 2 ;
(CnMIM)代表 1-垸基 -3-甲基咪唑阳离子（n为 1〜20的自然数）， 该材 料的具体制备步骤如下： (C n MIM) represents 1-mercapto-3-methylimidazolium cation (n is a natural number of 1 to 20), and the specific preparation steps of the material are as follows:
1 ) 按照溴化 1-十四垸基 -3甲基咪唑离子液体 ([C14MIM]Br)与 α- 憐酸氨钛的摩尔比为 1 : 10的比例来称料； 1) weighing according to a ratio of 1:10 in a molar ratio of 1-tetradecyl-3-methylimidazolium ionic liquid ([C 14 MIM]Br) to α-diuretic ammonia titanium;
本实施例所述的离子液体为： 咪唑离子液体。咪唑离子液体的常 规合成工艺得到， 是本专业技术人员可以实施的， 例如由垸基咪唑阳 离子和 F―、 Cl—、 Br―、 I—阴离子， 按照常规工艺组合得到卤化垸基咪 唑离子液体； The ionic liquid described in this embodiment is: an imidazole ionic liquid. The conventional synthetic process of imidazolium ionic liquid can be carried out by a person skilled in the art, for example, by a combination of a mercapto imidazolium cation and an F-, Cl-, Br-, I-anion, according to a conventional process to obtain a halogenated mercapto imidazolium ionic liquid;
无机载体材料为 α-憐酸氨钛 （分子结构式为 Τί(ΝΗ4Ρ04)2·Η20)， 其合成过程为： α-憐酸氢钛与氨水按照摩尔比 1:10〜10:1混合， a-憐 酸氢钛层板 -ΟΗ基团上的 Η+被 ΝΗ4 +取代得到 a-憐酸氨钛， 都是采用 本专业技术人员熟知的合成工艺。 The inorganic carrier material is α-pure acid ammonia titanium (the molecular structural formula is Τί(ΝΗ 4 Ρ0 4 ) 2 ·Η 2 0), and the synthesis process thereof is: α-pity hydrogen titanium and ammonia water in a molar ratio of 1:10~10: 1 mixing, a-pure acid hydrogen titanium laminate - Η on the fluorene group + ΝΗ 4 + substitution to obtain a-diuretic ammonia titanium, using a synthetic process well known to those skilled in the art.
2 ) 在常压下将步骤 1 ) 称取的溴化 1-十四垸基 -3甲基咪唑离子 液体与 α-憐酸氨钛放入温度为 20°C的溶剂中混合， 其中， 混合比例 为所称取的溴化 1-十四垸基 -3甲基咪唑离子液体和 a-憐酸氨钛的总 量与溶剂的质量比为 1:1的比例混合， 搅拌反应 72小时， 离子液体 的 1-十四垸基 -3甲基咪唑阳离子与 α -憐酸铵钛层板 -OH上的 H+发生 离子交换反应， 使离子液体得以进入到 α -憐酸铵钛的层间， 与层板
上的 -0—紧密结合合成了至完全反应得到溴化 1-十四垸基 -3甲基咪唑 离子液体插层 α-憐酸氨钛的耐热型复合抗菌功能材料溶液；离子液体 插层 α-憐酸氨钛的结构见图 1 ; 2) mixing the 1-tetradecyl-3-methylimidazolium ionic liquid weighed in step 1) with α-petic acid ammonia titanium in a solvent having a temperature of 20 ° C under normal pressure, wherein, mixing The ratio is the ratio of the total amount of the 1-tetradecyl-3-methylimidazolium ionic liquid of the bromide and the a-titanium titanium bromide 1:1, and the mass ratio of the solvent is 1:1, and the reaction is stirred for 72 hours. The liquid 1-tetradecyl-3methylimidazolium cation undergoes an ion exchange reaction with H + on the α - p-acid ammonium titanium plate-OH to allow the ionic liquid to enter the interlayer of the α - p-acid ammonium titanium. With laminate -0 - tightly combined to synthesize a heat-resistant composite antibacterial functional material solution to completely react to obtain 1-tetradecyl-3 methylimidazolium ionic liquid intercalated alpha-pure acid ammonia titanium; ionic liquid intercalation The structure of α-pure acid ammonia titanium is shown in Figure 1;
3 ) 然后将步骤 2 ) 得到的溴化 1-十四垸基 -3 甲基咪唑离子液体 插层 α-憐酸氨钛有机-无机复合抗菌材料溶液离心分离， 用水和乙醇 充分洗涤 （采用常规工艺）， 在常温常压下进行干燥， 获得白色粉末 状的溴化 1-十四垸基 -3 甲基咪唑离子液体插层 a-憐酸氨钛的复合抗 菌功能材料。 离子液体插层 a-憐酸氨钛的结构参见图 1， 其复合抗菌 功能材料得抗菌效果见表 2。 3) Then, the 1-tetradecyl-3 methylimidazolium ionic liquid obtained by the step 2) is intercalated into the α-pure acid ammonia titanium organic-inorganic composite antibacterial material solution, and is thoroughly washed with water and ethanol (using conventional The process is carried out by drying at normal temperature and normal pressure to obtain a composite antibacterial functional material of a white powdery 1-tetradecyl-3-methylimidazolium ionic liquid intercalation layer a-diuretic ammonia titanium. The structure of the ionic liquid intercalation a-pure ammonia titanium is shown in Figure 1. The antibacterial effect of the composite antibacterial functional material is shown in Table 2.
本实施例中使用的溶剂为水占总体积的 10%; 乙醇占总体积的 The solvent used in this embodiment is 10% of the total volume of water; ethanol accounts for the total volume
90% 90%
本实施例还可以采用溴化 1-十六垸基 -3-甲基咪唑离子液体， 按 照上述反应步骤， 得到氯化 1-辛基 -3-甲基咪唑离子液体插层 α -憐 酸铵钛复合抗菌材料。 In this embodiment, a 1-hexyl-3-methylimidazolium ionic liquid can also be used, and according to the above reaction step, a 1-octyl-3-methylimidazolium ionic liquid intercalation layer α-o-acid ammonium salt can be obtained. Titanium composite antibacterial material.
本实施例还可以采用溴化 1-十八垸基 -3-甲基咪唑离子液体， 按 照上述反应步骤， 得到氯化 1-十八垸基 -3-甲基咪唑离子液体插层 α -憐酸铵钛复合抗菌材料。 In this embodiment, the 1-octadecyl-3-methylimidazolium ionic liquid can also be used, and according to the above reaction step, the 1-octadecyl-3-methylimidazolium ionic liquid intercalation layer α-pity is obtained. Ammonium ammonium phosphate composite antibacterial material.
实施例 2-6的合成方法及制备工艺与实施例 1相同，仅原料种类 和摩尔配比、溶剂种类和配比、反应时间和反应温度不同于实施例 1， 具体条件见表 1。 表 1 实施例列表 The synthesis method and preparation process of Examples 2 to 6 were the same as those in Example 1, except that the raw material type and the molar ratio, the solvent type and ratio, the reaction time and the reaction temperature were different from those in Example 1, and the specific conditions are shown in Table 1. Table 1 List of examples
实施例 离子液体 (离子液体 离子液体： 反应温度 反应时间 的名称 +α -憐酸 α -憐酸铵 (°C) (h) 铵钛）：溶 钛（摩尔 EXAMPLES Ionic Liquid (Ionic Liquid Ionic Liquid: Reaction Temperature Name of Reaction Time +α - Pity Acid α - Ammonium Ammonium (°C) (h) Ammonium Titanium): Dissolved Titanium (Moore
剂 （质量 比） Agent (mass ratio)
比） Than)
1 溴化 1-十 1 : 10 1 : 2 60 72 四垸基 -3- 甲基咪唑 1 Bromide 1-ten 1 : 10 1 : 2 60 72 tetradecyl-3-methylimidazole
2 溴化 1-十 1 : 100 1 : 4 70 36
六烧基 _3_ 2 Bromide 1-tend 1: 100 1 : 4 70 36 Six burning base _3_
甲基咪唑 Methylimidazole
3 溴化 1-十 1:1000 10:1 30 24 八垸基 -3- 甲基咪唑 3 Bromide 1-ten 1:1000 10:1 30 24 octadecyl-3-methylimidazole
4 氯化 1-十 1:1000 1:10 20 64 四垸基 -3- 甲基咪唑 4 Chlorinated 1-ten 1:1000 1:10 20 64 tetradecyl-3-methylimidazole
5 1-十六垸 1:300 1:5 60 48 基 -3-甲基 5 1-16垸 1:300 1:5 60 48 base-3-methyl
咪唑六氟 Imidazole hexafluoride
憐酸盐 Pity salt
6 1-十八垸 1:100 10:1 90 12 基 -3-甲基 6 1-18垸 1:100 10:1 90 12 base-3-methyl
咪唑四氟 Imidazole tetrafluoro
硼酸盐 Borate
抗菌性能检测 Antibacterial performance test
采用抑菌环试验法对复合材料进行抗菌活性检测。 The antibacterial activity of the composite was tested by the inhibition loop test method.
表 2 离子液体的抑菌活性 Table 2 Antibacterial activity of ionic liquids
酸铵钛复合抗菌材料 Ammonium ammonium titanium composite antibacterial material
实施例 4 氯化 1-十四垸基 -3- 8. 1 7. 9 Example 4 Chlorination 1-tetradecyl -3- 8. 1 7. 9
甲基咪唑插层 α -憐 Methylimidazole intercalation
酸铵钛复合抗菌材料 Ammonium ammonium titanium composite antibacterial material
实施例 5 1-十六垸基 -3-甲基 8. 4 8. 1 Example 5 1-hexadecanyl-3-methyl 8. 4 8. 1
咪唑六氟憐酸盐插层 Imidazolium hexafluoroacetate intercalation
α -憐酸铵钛复合抗 --pure acid ammonium titanium composite anti-
菌材料 Bacterial material
实施例 6 1-十八垸基 -3-甲基 7. 1 7. 3 Example 6 1-octadecyl-3-methyl 7. 1 7. 3
咪唑四氟硼酸盐插层 Imidazole tetrafluoroborate intercalation
α -憐酸铵钛复合抗 --pure acid ammonium titanium composite anti-
菌材料 Bacterial material
阴性对 α-憐酸铵钛 0 0 Negative pair α-pure ammonium titanium 0 0
眧 眧
评价方法为： 抑菌环直径大于 7mm， 判为有抑菌作用； 抑菌环直 径小于等于 7mm， 判为无抑菌作用。 The evaluation method is as follows: The diameter of the inhibition zone is greater than 7 mm, which is judged to have a bacteriostatic effect; the diameter of the inhibition zone is less than or equal to 7 mm, and is judged to have no bacteriostatic effect.
在实施例 2中的溶剂可以采用水和乙醇混合物， 水所占的体积比例 为 90%; 乙醇所占的比例为 10%, 或者水所占的体积比例为 95%; 乙醇所占的比例为 5%等均可以，这也是本领域技术人员可以胜任的。
The solvent in the second embodiment may be a mixture of water and ethanol, the volume ratio of water is 90%; the proportion of ethanol is 10%, or the proportion of water is 95%; the proportion of ethanol is 5% and the like are all possible, which is also competent to those skilled in the art.
Claims
1、一种耐热型复合抗菌功能材料， 其特征在于： 其为离子液体与 α-憐酸氨钛进行插层组装合成得到耐热型复合抗菌功能材料，所述的 耐热型复合抗菌功能材料的化学通式如下： Ti(A)b(P04)2; A heat-resistant composite antibacterial functional material, characterized in that: the ionic liquid and the α-pure acid ammonia titanium are intercalated and assembled to obtain a heat-resistant composite antibacterial functional material, and the heat-resistant composite antibacterial function The chemical formula of the material is as follows: Ti(A) b (P0 4 ) 2;
其中， 式中 A代表离子液体的阳离子, b为 1或 2; Wherein A represents a cation of an ionic liquid, and b is 1 or 2;
所述的离子液体为： 咪唑离子液体。 The ionic liquid is: an imidazole ionic liquid.
2、根据权利要求 1所述的耐热型复合抗菌功能材料的制备方法， 其特征在于： 所述的 α-憐酸氨钛是由： a-憐酸氢钛与氨水按照摩尔比 为 1 :10〜10:1混合， 采用合成工艺将 α-憐酸氢钛层板 -ΟΗ基团上的 Η+被 ΝΗ4 +取代而制得的 a-憐酸氨钛。 The method for preparing a heat-resistant composite antibacterial functional material according to claim 1, wherein: the α-pure acid ammonia titanium is composed of: a-distilled acid hydrogen titanium and ammonia water in a molar ratio of 1: 10~10: 1 mixing, the synthetic process Η on α- pity bicarbonate titanium lamina -ΟΗ group ΝΗ 4 + + is obtained by substitution of amino acid a- pity titanium.
3、 一种耐热型复合抗菌功能材料的制备方法， 其特征在于， 包 括以下步骤： 3. A method for preparing a heat-resistant composite antibacterial functional material, characterized in that it comprises the following steps:
1 )按照离子液体与无机载体的摩尔比为 1 :10〜10:1的比例配料； 其中， 所述的离子液体为： 咪唑离子液体； 1) according to the ratio of the ionic liquid to the inorganic carrier molar ratio of 1: 10~10:1; wherein, the ionic liquid is: imidazole ionic liquid;
2 ) 在常压下将步骤 1 ) 称取的离子液体与无机载体材料， 放入 温度为 20°C〜90°C的溶剂中， 按所称取离子液体和无机载体材料的 总量与溶剂以 1:1〜1:1000的质量比混合搅拌反应， 反应时间为 2小 时〜 72小时， 至完全反应后， 得到离子液体插层 α-憐酸氨钛耐热型 复合抗菌功能材料溶液； 2) The ionic liquid and the inorganic carrier material weighed in step 1) are placed in a solvent at a temperature of 20 ° C to 90 ° C under normal pressure, and the total amount of the ionic liquid and the inorganic carrier material and the solvent are weighed. The mixture is stirred at a mass ratio of 1:1 to 1:1000, and the reaction time is from 2 hours to 72 hours, and after complete reaction, an ionic liquid intercalation α-pure acid ammonia titanium heat-resistant composite antibacterial functional material solution is obtained;
3 )然后将步骤 2 )得到的有机-无机复合抗菌材料溶液离心分离， 用水和乙醇充分洗涤， 在常温常压下进行真空干燥， 得到粉末状的离 子液体插层 α-憐酸氨钛耐热型复合抗菌功能材料。 3) Then, the organic-inorganic composite antibacterial material solution obtained in the step 2) is centrifuged, washed thoroughly with water and ethanol, and vacuum-dried at normal temperature and normal pressure to obtain a powdery ionic liquid intercalation layer α-pure acid ammonia titanium heat-resistant Type composite antibacterial functional material.
4、根据权利要求 3所述的耐热型复合抗菌功能材料的制备方法， 其特征在于：所述的离子液体与 a-憐酸氨钛配料比例，优选离子液体 与 α-憐酸氨钛的摩尔比为 1 : 1〜1 : 2。 The method for preparing a heat-resistant composite antibacterial functional material according to claim 3, characterized in that the ratio of the ionic liquid to the a-pure acid ammonia titanium compound is preferably an ionic liquid and an alpha-pure acid ammonia titanium. The molar ratio is 1: 1~1: 2.
5、根据权利要求 3所述的耐热型复合抗菌功能材料的制备方法， 其特征在于： 所述的 α-憐酸氨钛是由： a-憐酸氢钛与氨水按照摩尔比 为 1 :10〜10:1混合， 采用合成工艺将 α-憐酸氢钛层板 -ΟΗ基团上的 Η+被 ΝΗ4 +取代而制得的 a-憐酸氨钛。 The method for preparing a heat-resistant composite antibacterial functional material according to claim 3, wherein: the α-pure acid ammonia titanium is: a-digestive hydrogen titanium and ammonia water in a molar ratio of 1: 10~10: 1 mixing, the synthetic process Η on α- pity bicarbonate titanium lamina -ΟΗ group ΝΗ 4 + + is obtained by substitution of amino acid a- pity titanium.
6、根据权利要求 3所述的耐热型复合抗菌功能材料的制备方法， 其特征在于： 在步骤 2) 中所述的溶剂为水和乙醇的混合物， 其中， 水占总体积的 10〜90%； 乙醇占总体积的 10〜90%。 The method for preparing a heat-resistant composite antibacterial functional material according to claim 3, wherein the solvent in the step 2) is a mixture of water and ethanol, wherein Water accounts for 10~90% of the total volume; ethanol accounts for 10~90% of the total volume.
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| CN102007910A (en) | 2011-04-13 |
| CN102007910B (en) | 2013-06-05 |
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