CN111234507A - Preparation method of TiO2PU composite material - Google Patents
Preparation method of TiO2PU composite material Download PDFInfo
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- CN111234507A CN111234507A CN202010207878.8A CN202010207878A CN111234507A CN 111234507 A CN111234507 A CN 111234507A CN 202010207878 A CN202010207878 A CN 202010207878A CN 111234507 A CN111234507 A CN 111234507A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004814 polyurethane Substances 0.000 claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 claims abstract description 44
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 41
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 33
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005642 Oleic acid Substances 0.000 claims abstract description 33
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- 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
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- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明公开了一种TiO2PU复合材料的制备方法，包括纳米TiO2、油酸、乙醇、丙酮和聚氨酯乳液，其制备步骤大致为：通过在丙酮中，加入适量油酸与纳米TiO2，混合分散搅拌后，进行抽滤以及丙酮洗涤，烘干研磨制得油酸改性纳米TiO2粉末，在将适量聚氨酯乳液和咪唑添加到50mL烧杯中，混合搅拌后加入3.5g甲基四氢苯酐固化剂，继续搅拌，通过真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体，将适量油酸改性纳米TiO2和前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，超声波分散反应后依次加入适量咪唑和甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料具有结构稳定、抗冲击性强、抗拉伸性强以及导电性强的优点。The invention discloses a preparation method of TiO2PU composite material, which comprises nano-TiO2, oleic acid, ethanol, acetone and polyurethane emulsion. , carry out suction filtration and acetone washing, drying and grinding to obtain oleic acid modified nano-TiO2 powder, add an appropriate amount of polyurethane emulsion and imidazole into a 50mL beaker, add 3.5g methyltetrahydrophthalic anhydride curing agent after mixing and stirring, and continue to stir , remove the bubbles by a vacuum filter pump, program the temperature to solidify, and prepare a polyurethane matrix, add an appropriate amount of oleic acid modified nano-TiO2 and the aforementioned polyurethane matrix into a beaker containing 50 mL of acetone, and then add an appropriate amount of imidazole and methyl alcohol after the ultrasonic dispersion reaction. base tetrahydrophthalic anhydride for stirring, vacuum filter pump to remove air bubbles in the system, and the glue liquid is cured at programmed temperature in an oven. Strong advantage.
Description
技术领域technical field
本发明公开了一种TiO2PU复合材料的制备方法，属于TiO2PU复合材料制备技术领域。The invention discloses a preparation method of TiO2PU composite material, and belongs to the technical field of TiO2PU composite material preparation.
背景技术Background technique
传统涂料能挥发有机挥发物(VOC)，影响环境和人们身体健康，水性涂料代替传统涂料成为未来涂料工业发展的必然趋势；Traditional coatings can volatilize volatile organic compounds (VOC), which affect the environment and people's health.
聚氨酯(PU)作为一种性能优良的功能性高分子材料，具有密度低、高弹性、耐磨性和柔韧性强的特点，广泛应用于涂料、胶黏剂、医用材料、食品包装以及日用鞋服等领域。但其亦存在一些不足，比如热稳定性差、机械性能不强等缺陷。为改善聚氨酯性能，常常采用纳米材料改性聚氨酯制得复合材料以提高其综合性能。常用的纳米材料有纳米TiO2、纳米炭黑、纳米SiO2等无机材料，目前，纳米TiO2改性聚氨酯复合材料成为人们研究水性涂料的重要成膜物质，然而传统的TiO2PU复合材料结构不稳定，导电性差以及抗拉伸能力较弱，无法满足需求，因此本发明新型提出一种TiO2PU复合材料的制备方法。As a functional polymer material with excellent performance, polyurethane (PU) has the characteristics of low density, high elasticity, wear resistance and flexibility, and is widely used in coatings, adhesives, medical materials, food packaging and daily use. Footwear and other fields. However, it also has some shortcomings, such as poor thermal stability and weak mechanical properties. In order to improve the properties of polyurethane, nanomaterials are often used to modify polyurethane to make composite materials to improve their comprehensive properties. Commonly used nano-materials include nano-TiO2, nano-carbon black, nano-SiO2 and other inorganic materials. At present, nano-TiO2-modified polyurethane composites have become an important film-forming material for water-based coatings. However, traditional TiO2PU composites have unstable structures and poor conductivity. And the tensile strength is weak, which cannot meet the demand, so the present invention provides a new preparation method of TiO2PU composite material.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是克服现有技术问题，提供一种TiO2PU复合材料的制备方法，从而解决上述问题。The technical problem to be solved by the present invention is to overcome the problems of the prior art and provide a preparation method of a TiO2PU composite material, thereby solving the above problems.
为实现上述目的，本发明提供如下技术方案：一种TiO2PU复合材料的制备方法，包括纳米TiO2、油酸、乙醇、丙酮和聚氨酯乳液，制备步骤为：In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of TiO2PU composite material, comprising nano-TiO2, oleic acid, ethanol, acetone and polyurethane emulsion, and the preparation steps are:
(1)油酸改性纳米TiO2：(1) Oleic acid modified nano-TiO2:
在40mL的丙酮中，加入6g油酸与10g纳米TiO2，充分混合，调节pH值7～7.5，通过超声波清洗器55℃超声波分散30min，回流状态下高速均质分散机上以4000r/min速度搅拌5h，抽滤，丙酮洗涤，温度升至80℃，烘干3h，研磨，制得油酸改性纳米TiO2粉末；In 40mL of acetone, add 6g of oleic acid and 10g of nano-TiO2, mix well, adjust the pH value to 7-7.5, disperse by ultrasonic wave at 55°C for 30min, and stir at 4000r/min speed for 5h on a high-speed homogenizer under reflux. , suction filtered, washed with acetone, the temperature was raised to 80 °C, dried for 3 h, and ground to obtain oleic acid modified nano-TiO2 powder;
(2)聚合物基体的制备：(2) Preparation of polymer matrix:
将2.0g的聚氨酯乳液和0.3g咪唑添加到50mL烧杯中，80℃水浴温度下搅拌1h，温度降到53～56℃后，加入3.5g甲基四氢苯酐固化剂，继续搅拌2～3h，待咪唑完全溶解后，真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体；Add 2.0g of polyurethane emulsion and 0.3g of imidazole to a 50mL beaker, stir at 80°C water bath temperature for 1h, after the temperature drops to 53-56°C, add 3.5g of methyltetrahydrophthalic anhydride curing agent, continue stirring for 2-3h, After the imidazole is completely dissolved, the vacuum filter pump removes the bubbles, and the temperature is programmed to solidify to obtain the polyurethane matrix;
(3)TiO2/PU复合材料的制备：(3) Preparation of TiO2/PU composites:
将1.0g油酸改性纳米TiO2和3.0g前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，80℃水浴温度下超声波分散反应，温度降到53～56℃后，依次加入0.2g咪唑和2.5g甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料。Add 1.0g of oleic acid modified nano-TiO2 and 3.0g of the aforementioned polyurethane matrix into a beaker filled with 50mL of acetone, and ultrasonically disperse the reaction at a water bath temperature of 80°C. After the temperature drops to 53 to 56°C, add 0.2g of imidazole and 2.5 g methyl tetrahydrophthalic anhydride is stirred, the air bubbles in the system are removed by a vacuum filter pump, and the glue solution is cured at a programmed temperature in an oven, and a TiO2/PU composite material is obtained after curing.
作为优选，所述超声波清洗器的型号为SK1200H型。Preferably, the model of the ultrasonic cleaner is SK1200H.
作为优选，所述高速均质分散机的型号为FJ-200型。Preferably, the model of the high-speed homogenizer disperser is FJ-200.
作为优选，所述油酸改性纳米TiO2和前述聚氨酯基体在80℃水浴温度下超声波分散反应2～3h。Preferably, the oleic acid-modified nano-TiO2 and the aforementioned polyurethane matrix are subjected to ultrasonic dispersion reaction at a water bath temperature of 80° C. for 2-3 hours.
作为优选，所述咪唑和甲基四氢苯酐需要混合搅拌1～2h。Preferably, the imidazole and methyl tetrahydrophthalic anhydride need to be mixed and stirred for 1-2 hours.
作为优选，所述低碳醇为碳原子数为C3的低碳醇。Preferably, the low-carbon alcohol is a low-carbon alcohol with a carbon number of C3.
作为优选，所述烘箱内的固化温度和时间设置为：90℃/3h+110℃/2h+140℃/1h+160℃/1h。Preferably, the curing temperature and time in the oven are set to: 90°C/3h+110°C/2h+140°C/1h+160°C/1h.
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
本发明通过在丙酮中，加入适量油酸与纳米TiO2，混合分散搅拌后，进行抽滤以及丙酮洗涤，烘干研磨制得油酸改性纳米TiO2粉末，在将适量聚氨酯乳液和咪唑添加到50mL烧杯中，混合搅拌后加入3.5g甲基四氢苯酐固化剂，继续搅拌，通过真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体，将适量油酸改性纳米TiO2和前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，超声波分散反应后依次加入适量咪唑和甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料具有结构稳定、抗冲击性强、抗拉伸性强以及导电性强的优点。In the present invention, oleic acid modified nano-TiO2 powder is prepared by adding an appropriate amount of oleic acid and nano-TiO2 into acetone, and after mixing, dispersing and stirring, performing suction filtration, washing with acetone, drying and grinding to obtain oleic acid-modified nano-TiO2 powder, and adding an appropriate amount of polyurethane emulsion and imidazole to 50 mL In the beaker, add 3.5g of methyl tetrahydrophthalic anhydride curing agent after mixing and stirring, continue to stir, remove air bubbles through a vacuum filter pump, program the temperature to solidify, and prepare a polyurethane matrix, add an appropriate amount of oleic acid modified nano-TiO2 and the aforementioned polyurethane matrix into In a beaker filled with 50 mL of acetone, after ultrasonic dispersion reaction, an appropriate amount of imidazole and methyltetrahydrophthalic anhydride were added in turn for stirring, and a vacuum filter pump removed air bubbles in the system. PU composite material has the advantages of stable structure, strong impact resistance, strong tensile resistance and strong electrical conductivity.
具体实施方式Detailed ways
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1：一种TiO2PU复合材料的制备方法，包括纳米TiO2、油酸、乙醇、丙酮和聚氨酯乳液，制备步骤为：Embodiment 1: a preparation method of TiO2PU composite material, including nano-TiO2, oleic acid, ethanol, acetone and polyurethane emulsion, the preparation steps are:
(1)油酸改性纳米TiO2：(1) Oleic acid modified nano-TiO2:
在40mL的丙酮中，加入6g油酸与10g纳米TiO2，充分混合，调节pH值7～7.5，通过超声波清洗器55℃超声波分散30min，回流状态下高速均质分散机上以4000r/min速度搅拌5h，抽滤，丙酮洗涤，温度升至80℃，烘干3h，研磨，制得油酸改性纳米TiO2粉末；In 40mL of acetone, add 6g of oleic acid and 10g of nano-TiO2, mix well, adjust the pH value to 7-7.5, disperse by ultrasonic wave at 55°C for 30min, and stir at 4000r/min speed for 5h on a high-speed homogenizer under reflux. , suction filtered, washed with acetone, the temperature was raised to 80 °C, dried for 3 h, and ground to obtain oleic acid modified nano-TiO2 powder;
(2)聚合物基体的制备：(2) Preparation of polymer matrix:
将2.0g的聚氨酯乳液和0.3g咪唑添加到50mL烧杯中，80℃水浴温度下搅拌1h，温度降到53～56℃后，加入3.5g甲基四氢苯酐固化剂，继续搅拌2～3h，待咪唑完全溶解后，真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体；Add 2.0g of polyurethane emulsion and 0.3g of imidazole to a 50mL beaker, stir at 80°C water bath temperature for 1h, after the temperature drops to 53-56°C, add 3.5g of methyltetrahydrophthalic anhydride curing agent, continue stirring for 2-3h, After the imidazole is completely dissolved, the vacuum filter pump removes the bubbles, and the temperature is programmed to solidify to obtain the polyurethane matrix;
(3)TiO2/PU复合材料的制备：(3) Preparation of TiO2/PU composites:
将1.0g油酸改性纳米TiO2和3.0g前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，80℃水浴温度下超声波分散反应，温度降到53～56℃后，依次加入0.2g咪唑和2.5g甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料。Add 1.0g of oleic acid modified nano-TiO2 and 3.0g of the aforementioned polyurethane matrix into a beaker filled with 50mL of acetone, and ultrasonically disperse the reaction at a water bath temperature of 80°C. After the temperature drops to 53 to 56°C, add 0.2g of imidazole and 2.5 g methyl tetrahydrophthalic anhydride is stirred, the air bubbles in the system are removed by a vacuum filter pump, and the glue solution is cured at a programmed temperature in an oven, and a TiO2/PU composite material is obtained after curing.
其中，所述超声波清洗器的型号为SK1200H型。Wherein, the model of the ultrasonic cleaner is SK1200H.
其中，所述高速均质分散机的型号为FJ-200型。Wherein, the model of the high-speed homogenizer disperser is FJ-200.
其中，所述油酸改性纳米TiO2和前述聚氨酯基体在80℃水浴温度下超声波分散反应2～3h。Wherein, the oleic acid-modified nano-TiO2 and the aforementioned polyurethane matrix are subjected to ultrasonic dispersion reaction at a water bath temperature of 80° C. for 2-3 hours.
其中，所述咪唑和甲基四氢苯酐需要混合搅拌1～2h。Wherein, the imidazole and methyl tetrahydrophthalic anhydride need to be mixed and stirred for 1-2 hours.
其中，所述低碳醇为碳原子数为C3的低碳醇。Wherein, the low-carbon alcohol is a low-carbon alcohol whose carbon number is C3.
其中，所述烘箱内的固化温度和时间设置为：90℃/3h+110℃/2h+140℃/1h+160℃/1h。Wherein, the curing temperature and time in the oven are set as: 90°C/3h+110°C/2h+140°C/1h+160°C/1h.
实施例2：一种TiO2PU复合材料的制备方法，包括纳米TiO2、油酸、乙醇、丙酮和聚氨酯乳液，制备步骤为：Embodiment 2: a preparation method of TiO2PU composite material, including nano-TiO2, oleic acid, ethanol, acetone and polyurethane emulsion, the preparation steps are:
(1)油酸改性纳米TiO2：(1) Oleic acid modified nano-TiO2:
在40mL的丙酮中，加入6g油酸与10g纳米TiO2，充分混合，调节pH值7～7.5，通过超声波清洗器55℃超声波分散30min，回流状态下高速均质分散机上以4000r/min速度搅拌5h，抽滤，丙酮洗涤，温度升至80℃，烘干3h，研磨，制得油酸改性纳米TiO2粉末；In 40mL of acetone, add 6g of oleic acid and 10g of nano-TiO2, mix well, adjust the pH value to 7-7.5, disperse by ultrasonic wave at 55°C for 30min, and stir at 4000r/min speed for 5h on a high-speed homogenizer under reflux. , suction filtered, washed with acetone, the temperature was raised to 80 °C, dried for 3 h, and ground to obtain oleic acid modified nano-TiO2 powder;
(2)聚合物基体的制备：(2) Preparation of polymer matrix:
将2.0g的聚氨酯乳液和0.3g咪唑添加到50mL烧杯中，80℃水浴温度下搅拌1h，温度降到53～56℃后，加入3.5g甲基四氢苯酐固化剂，继续搅拌2～3h，待咪唑完全溶解后，真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体；Add 2.0g of polyurethane emulsion and 0.3g of imidazole to a 50mL beaker, stir at 80°C water bath temperature for 1h, after the temperature drops to 53-56°C, add 3.5g of methyltetrahydrophthalic anhydride curing agent, continue stirring for 2-3h, After the imidazole is completely dissolved, the vacuum filter pump removes the bubbles, and the temperature is programmed to solidify to obtain the polyurethane matrix;
(3)TiO2/PU复合材料的制备：(3) Preparation of TiO2/PU composites:
将3.0g油酸改性纳米TiO2和3.0g前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，80℃水浴温度下超声波分散反应，温度降到53～56℃后，依次加入0.2g咪唑和2.5g甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料。Add 3.0g of oleic acid modified nano-TiO2 and 3.0g of the aforementioned polyurethane matrix into a beaker filled with 50mL of acetone, and ultrasonically disperse the reaction at a water bath temperature of 80°C. After the temperature drops to 53 to 56°C, add 0.2g of imidazole and 2.5 g methyl tetrahydrophthalic anhydride is stirred, the air bubbles in the system are removed by a vacuum filter pump, and the glue solution is cured at a programmed temperature in an oven, and a TiO2/PU composite material is obtained after curing.
其中，所述超声波清洗器的型号为SK1200H型。Wherein, the model of the ultrasonic cleaner is SK1200H.
其中，所述高速均质分散机的型号为FJ-200型。Wherein, the model of the high-speed homogenizer disperser is FJ-200.
其中，所述油酸改性纳米TiO2和前述聚氨酯基体在80℃水浴温度下超声波分散反应2～3h。Wherein, the oleic acid-modified nano-TiO2 and the aforementioned polyurethane matrix are subjected to ultrasonic dispersion reaction at a water bath temperature of 80° C. for 2-3 hours.
其中，所述咪唑和甲基四氢苯酐需要混合搅拌1～2h。Wherein, the imidazole and methyl tetrahydrophthalic anhydride need to be mixed and stirred for 1-2 hours.
其中，所述低碳醇为碳原子数为C3的低碳醇。Wherein, the low-carbon alcohol is a low-carbon alcohol whose carbon number is C3.
其中，所述烘箱内的固化温度和时间设置为：90℃/3h+110℃/2h+140℃/1h+160℃/1h。Wherein, the curing temperature and time in the oven are set as: 90°C/3h+110°C/2h+140°C/1h+160°C/1h.
实施例3：一种TiO2PU复合材料的制备方法，包括纳米TiO2、油酸、乙醇、丙酮和聚氨酯乳液，制备步骤为：Embodiment 3: a preparation method of TiO2PU composite material, including nano-TiO2, oleic acid, ethanol, acetone and polyurethane emulsion, the preparation steps are:
(1)油酸改性纳米TiO2：(1) Oleic acid modified nano-TiO2:
在40mL的丙酮中，加入6g油酸与10g纳米TiO2，充分混合，调节pH值7～7.5，通过超声波清洗器55℃超声波分散30min，回流状态下高速均质分散机上以4000r/min速度搅拌5h，抽滤，丙酮洗涤，温度升至80℃，烘干3h，研磨，制得油酸改性纳米TiO2粉末；In 40mL of acetone, add 6g of oleic acid and 10g of nano-TiO2, mix well, adjust the pH value to 7-7.5, disperse by ultrasonic wave at 55°C for 30min, and stir at 4000r/min speed for 5h on a high-speed homogenizer under reflux. , suction filtered, washed with acetone, the temperature was raised to 80 °C, dried for 3 h, and ground to obtain oleic acid modified nano-TiO2 powder;
(2)聚合物基体的制备：(2) Preparation of polymer matrix:
将2.0g的聚氨酯乳液和0.3g咪唑添加到50mL烧杯中，80℃水浴温度下搅拌1h，温度降到53～56℃后，加入3.5g甲基四氢苯酐固化剂，继续搅拌2～3h，待咪唑完全溶解后，真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体；Add 2.0g of polyurethane emulsion and 0.3g of imidazole to a 50mL beaker, stir at 80°C water bath temperature for 1h, after the temperature drops to 53-56°C, add 3.5g of methyltetrahydrophthalic anhydride curing agent, continue stirring for 2-3h, After the imidazole is completely dissolved, the vacuum filter pump removes the bubbles, and the temperature is programmed to solidify to obtain the polyurethane matrix;
(3)TiO2/PU复合材料的制备：(3) Preparation of TiO2/PU composites:
将1.5g油酸改性纳米TiO2和3.0g前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，80℃水浴温度下超声波分散反应，温度降到53～56℃后，依次加入0.2g咪唑和2.5g甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料。Add 1.5g of oleic acid modified nano-TiO2 and 3.0g of the aforementioned polyurethane matrix into a beaker containing 50mL of acetone, and ultrasonically disperse the reaction at a water bath temperature of 80°C. After the temperature drops to 53 to 56°C, add 0.2g of imidazole and 2.5 g methyl tetrahydrophthalic anhydride is stirred, the air bubbles in the system are removed by a vacuum filter pump, and the glue solution is cured at a programmed temperature in an oven, and a TiO2/PU composite material is obtained after curing.
其中，所述超声波清洗器的型号为SK1200H型。Wherein, the model of the ultrasonic cleaner is SK1200H.
其中，所述高速均质分散机的型号为FJ-200型。Wherein, the model of the high-speed homogenizer disperser is FJ-200.
其中，所述油酸改性纳米TiO2和前述聚氨酯基体在80℃水浴温度下超声波分散反应2～3h。Wherein, the oleic acid-modified nano-TiO2 and the aforementioned polyurethane matrix are subjected to ultrasonic dispersion reaction at a water bath temperature of 80° C. for 2-3 hours.
其中，所述咪唑和甲基四氢苯酐需要混合搅拌1～2h。Wherein, the imidazole and methyl tetrahydrophthalic anhydride need to be mixed and stirred for 1-2 hours.
其中，所述低碳醇为碳原子数为C3的低碳醇。Wherein, the low-carbon alcohol is a low-carbon alcohol whose carbon number is C3.
其中，所述烘箱内的固化温度和时间设置为：90℃/3h+110℃/2h+140℃/1h+160℃/1h。Wherein, the curing temperature and time in the oven are set as: 90°C/3h+110°C/2h+140°C/1h+160°C/1h.
具体的，本发明通过在丙酮中，加入适量油酸与纳米TiO2，混合分散搅拌后，进行抽滤以及丙酮洗涤，烘干研磨制得油酸改性纳米TiO2粉末，在将适量聚氨酯乳液和咪唑添加到50mL烧杯中，混合搅拌后加入3.5g甲基四氢苯酐固化剂，继续搅拌，通过真空滤气泵除去其中气泡，程序升温固化，制得聚氨酯基体，将适量油酸改性纳米TiO2和前述聚氨酯基体加入到盛有50mL丙酮的烧杯中，超声波分散反应后依次加入适量咪唑和甲基四氢苯酐进行搅拌，真空滤气泵除去体系中气泡，将胶液于烘箱中进行程序升温固化，固化后得到TiO2/PU复合材料具有结构稳定、抗冲击性强、抗拉伸性强以及导电性强的优点,其中，实施例123中油酸改性纳米TiO2中在材料中的占比为2％、6％、3％。Specifically, the present invention obtains oleic acid-modified nano-TiO2 powder by adding an appropriate amount of oleic acid and nano-TiO2 in acetone, mixing, dispersing and stirring, performing suction filtration, washing with acetone, drying and grinding to obtain oleic acid-modified nano-TiO2 powder, and mixing an appropriate amount of polyurethane emulsion and imidazole Add it to a 50mL beaker, add 3.5g of methyltetrahydrophthalic anhydride curing agent after mixing and stirring, continue to stir, remove air bubbles through a vacuum filter pump, program temperature for curing, and prepare a polyurethane matrix. The polyurethane matrix was added to a beaker containing 50 mL of acetone. After the ultrasonic dispersion reaction, an appropriate amount of imidazole and methyl tetrahydrophthalic anhydride were added in sequence for stirring. The vacuum filter pump removed the air bubbles in the system, and the glue was cured in an oven at programmed temperature. The obtained TiO2/PU composite material has the advantages of stable structure, strong impact resistance, strong tensile resistance and strong electrical conductivity. Among them, the proportion of oleic acid modified nano-TiO2 in the material in Example 123 is 2%, 6% %, 3%.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made in these embodiments without departing from the principle and spirit of the invention and modifications, the scope of the present invention is defined by the appended claims and their equivalents.
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