Aluminum-titanium bimetallic composite coupling agent and synthesis method thereof

Abstract

The synthesis method comprises the following steps: firstly, adding water and methanol as solvents into basic aluminum chloride and polyhydric alcohol according to a certain proportion, and reacting at 100-110 DEG C to synthesize an alcohol-aluminum complex; the method comprises the following steps: by taking short-chain alcohol as an organic solvent, adding aliphatic carboxylic acid and titanate, dissolving an alcohol-aluminum complex with methanol, adding the alcohol-aluminum complex into a reaction solution, and reacting at 100-110 DEG C to synthesize the aluminum-titanium bimetallic composite coupling agent. The synthesis method of the aluminum-titanium bimetallic composite coupling agent has the advantages of simple process and low cost, and has a good modification effect on an inorganic powder polymer composite material.

Description

Technical Field

[0001] The present invention relates to a coupling agent and its preparation process, and particularly to an aluminum-titanium bimetallic composite coupling agent and its synthesis method. Background Art

[0002] In the polymer material system, there are differences in chemical structure and physical form between micron- and nano-scale inorganic fillers and the matrix, and there is a lack of affinity between them.

[0003] Generally, the filler can only play the role of increasing the amount. At the same time, due to excessive filling of inorganic fillers, the viscosity of the polymer composite in the viscous flow state will increase significantly, resulting in poor processing performance of the material. In addition, since it is not easy to mix the nano-filler and the polymer evenly, the mechanical properties of the product will decrease, restricting the amount of filler used. For a long time, people have been paying attention to the surface modification of inorganic materials, trying to attach active organic groups to the surface of inorganic fillers to change the inherent hydrophilicity of the fillers, so as to improve the compatibility between nano-fillers and organic materials and the dispersibility of the fillers, which has promoted the emergence of many coupling agents.

[0004] A coupling agent is an important treatment agent with an increasingly wide range of application fields, mainly used as an additive for polymer composites. The most prominent feature of the molecular structure of the coupling agent is that the molecule contains two groups with different chemical properties: one is a group that is inorganic-philic and easily reacts with the surface of inorganic substances; the other is an organic-philic group that can react chemically with synthetic resins or other polymers or form hydrogen bonds and dissolve in them. Therefore, the coupling agent is called a "molecular bridge" to improve the interfacial interaction between inorganic and organic substances, thereby greatly improving the properties of the composite material, such as physical properties, electrical properties, thermal properties, optical properties, etc.

[0005] As a key material for improving the properties of polymer composites and reducing costs, coupling agents are widely applicable to industries such as plastics, rubber, glass fiber reinforced plastics, coatings, pigments, papermaking, adhesives, magnetic materials, oilfield chemicals, etc. With the continuous development of polymer blends and fillers, the demand for new multifunctional coupling agents is more urgent.

[0006] However, traditional single coupling agents have problems such as poor surface modification effect on inorganic fillers, complex production processes, and high costs. Summary of the Invention

[0007] The purpose of the present invention is to overcome the deficiencies of traditional single coupling agents, such as poor surface modification effect on inorganic fillers, complex processes, and high costs, and provide an aluminum-titanium bimetallic composite coupling agent and its synthesis method.

[0008] The present invention is achieved by the following technical solutions: A synthesis method of an aluminum-titanium bimetallic composite coupling agent, comprising the following steps: S1. Synthesize an alcohol-aluminum complex by a polymerization reaction using basic aluminum chloride and polyol as raw materials: Completely dissolve basic aluminum chloride in a mixed solution of water and methanol, heat to reflux, continue heating to 100 - 110 °C, add polyol, stir and react. After the reaction ends, filter the solution, distill off the solvent under reduced pressure to obtain a light yellow solid; dry the solid in an oven at 100 - 110 °C to obtain the required alcohol-aluminum complex; S2. Synthesize an aluminum-titanium bimetallic composite coupling agent using the alcohol-aluminum complex, isopropanol, titanate, fatty carboxylic acid, and methanol as raw materials: The mass ratio of titanate to aliphatic carboxylic acid is 1:3 - 1:12. Add the aliphatic carboxylic acid to isopropanol, stir and dissolve at room temperature. After complete dissolution, gradually add titanate and stir and reflux at 80 - 100 °C; dissolve the alcohol-aluminum complex in methanol by ultrasonic oscillation, add it to the above reaction solution, heat to 100 - 110 °C and continue the reaction. After the reaction ends, distill off the solvent under reduced pressure to obtain a light yellow solid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0009] In the above step S1, the polyol is any one of polyols with less than 5 carbon atoms.

[0010] In the above step S2, the titanate is ethyl titanate, isopropyl titanate, and / or butyl titanate.

[0011] In the above step S2, the aliphatic carboxylic acid can be a long-chain carboxylic acid, cycloalkane carboxylic acid, and / or unsaturated carboxylic acid with 1 - 18 carbon atoms.

[0012] In the above step S1, the mass ratio of basic aluminum chloride to water and methanol is 1:1:1.5; the mass ratio of basic aluminum chloride to polyol is 5:2.

[0013] In the above step S2, the reflux reaction temperature is 80 - 90 °C, the amount of methanol used is 10 - 20 mL; the mass ratios of titanate to aliphatic carboxylic acid are 1:3, 1:7, 1:9, and 1:12 respectively.

[0014] In the above step S2, the stirring and reflux reaction time at 80 - 100 °C is 1 - 2 hours.

[0015] In the above step S2, the time for continuing the reaction by heating to 100 - 110 °C is 1 - 2 hours; the ultrasonic oscillation time is 10 - 30 minutes.

[0016] In the above step S1, the stirring reaction time is 1 - 2 hours.

[0017] Compared with the prior art, the present invention has the following advantages and effects: The aluminum-titanium bimetallic coupling agent synthesized in the present invention contains a relatively large number of Al-O-C bonds and Ti-O-C bonds in its structure. Compared with single titanate and aluminate coupling agents, it combines the characteristics of both, can make up for the deficiencies of single coupling agents, and the existence of bimetallic binding points enables this type of coupling agent to better bind to the surface of inorganic fillers. Compared with other coupling agents (such as silane coupling agents), better effects can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is the infrared spectrogram of the aluminum-titanium bimetallic coupling agent. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] The present invention discloses an aluminum-titanium bimetallic composite coupling agent and its synthesis method. The following further specifically and detailedly describes the present invention in combination with specific embodiments.

[0020] Example 1: 40 g of basic aluminum chloride and 40 g of water were stirred in a three-necked flask equipped with a stirring and reflux device until completely dissolved, then 60 g of methanol solution was added, heated to 80 °C for reflux, and further heated to 110 °C. 16 g of 1,2-propanediol was added and stirred for reaction for 1 h. After the reaction ended, the solution was filtered, and the solvent was evaporated under reduced pressure to obtain a pale yellow solid. The solid was dried in an oven at 100 °C to obtain the required alcohol-aluminum complex.

[0021] Accurately weigh 21.3 g of stearic acid, add it to a three-necked flask, then add 30 mL of isopropanol, stir to completely dissolve it, and slowly dropwise add 7.11 g of isopropyl titanate. After reacting for 1 h at 90 °C, 3.1 g of the alcohol-aluminum complex was added to 20 mL of methanol, dissolved by ultrasonic oscillation for 30 min, added to the above reaction solution, heated to 110 °C, and continued to react for 1 h. The solvent was evaporated under reduced pressure to obtain a pale yellow solid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0022] Example 2: In this example, the synthesis conditions of the alcohol-aluminum complex are the same as those in Example 1.

[0023] Accurately weigh 42.6 g of stearic acid, add it to a three-necked flask, then add 40 mL of isopropanol, stir to completely dissolve it, and slowly dropwise add 7.11 g of isopropyl titanate. After reacting for 1 h at 90 °C, 3.1 g of the alcohol-aluminum complex was added to 20 mL of methanol, dissolved by ultrasonic oscillation for 30 min, added to the above reaction solution, heated to 110 °C, and continued to react for 1 h. The solvent was evaporated under reduced pressure to obtain a pale yellow solid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0024] Example 3: In this example, the synthesis conditions of the aluminum alcohol complex are the same as those in Example 1.

[0025] Accurately weigh 64 g of stearic acid and add it to a three-necked flask. Then add 50 mL of isopropanol and stir to completely dissolve it. Slowly add 7.11 g of isopropyl titanate dropwise. After reacting for 1 h at a temperature of 90 °C, add 3.1 g of the aluminum alcohol complex to 20 mL of methanol and dissolve it by ultrasonic oscillation for 30 min. Add it to the above reaction solution, heat to 110 °C, and continue to react for 1 h. Distill off the solvent under reduced pressure to obtain a light yellow solid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0026] Example 4: In this example, the synthesis conditions of the aluminum alcohol complex are the same as those in Example 1.

[0027] Accurately weigh 85.3 g of stearic acid and add it to a three-necked flask. Then add 60 mL of isopropanol and stir to completely dissolve it. Slowly add 7.11 g of isopropyl titanate dropwise. After reacting for 1 h at a temperature of 90 °C, add 3.1 g of the aluminum alcohol complex to 20 mL of methanol and dissolve it by ultrasonic oscillation for 30 min. Add it to the above reaction solution, heat to 110 °C, and continue to react for 1 h. Distill off the solvent under reduced pressure to obtain a light yellow solid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0028] Example 5: In this example, the synthesis conditions of the aluminum alcohol complex are the same as those in Example 1.

[0029] Accurately weigh 16.9 g of oleic acid and add it to a three-necked flask. Then add 30 mL of isopropanol and stir to completely dissolve it. Slowly add 7.11 g of isopropyl titanate dropwise. After reacting for 1 h at a temperature of 90 °C, add 2.5 g of the aluminum alcohol complex to 20 mL of methanol and dissolve it by ultrasonic oscillation for 30 min. Add it to the above reaction solution, heat to 110 °C, and continue to react for 1 h. Distill off the solvent under reduced pressure to obtain a brownish-yellow viscous liquid, which is the required aluminum-titanium bimetallic composite coupling agent.

[0030] Example 6: Experimental purpose: To compare the feasibility and effectiveness of synthesizing the aluminum-titanium bimetallic composite coupling agent of the present invention, in this example, the product synthesized in Example 1 is compared with a commercially available titanate coupling agent (GR-110, Nanjing Herun Coupling Agent Co., Ltd.), and a performance comparison experiment is carried out with a calcium carbonate powder-filled PP composite material as the experimental object.

[0031] Experimental method: Surface treatment of calcium carbonate powder: Add calcium carbonate powder to a stirrer, heat to 80 °C, add a coupling agent with a dosage of 1%, raise the temperature to 105 °C, stir thoroughly for 2 h, discharge, and dry in an oven at 100 °C to obtain the treated calcium carbonate powder.

[0032] Preparation of composite material: Mix the treated calcium carbonate powder with polypropylene, melt and process in a two-roll mill to form a composite sheet, cut samples, and prepare test specimens.

[0033] Testing of material properties: Test the mechanical properties of the prepared specimens.

[0034] Tensile testing is carried out according to the standard of GB / T 1040-2006, impact testing is carried out according to the standard of GB / T 1043.1-2008, and bending testing is carried out according to the standard of GB / T 9341-2008.

[0035] Experimental results: Table 1 Influence of surface treatment agent on the properties of calcium carbonate / PP composite materials (calcium carbonate content 5%)

[0036] It can be seen from the data in Table 1 that the impact strength, flexural strength, tensile strength, and elongation at break of Example 1 are all higher than those of the unmodified composite material and the comparative examples, and the treatment effect is better. The synthesis process of the coupling agent of the present invention is simple, the cost is low, the treatment effect on the filler is obvious, it can effectively improve the interfacial interaction between the inorganic filler and the organic polymer, improve the comprehensive performance of the composite material, and is suitable for industrial application and promotion.

[0037] Figure 1 It is the infrared spectrum of the coupling agent synthesized in Example 1. The absorption peak at 3409 cm -1 is the characteristic peak of -OH; the absorption peaks at 2921 cm -1 , 2849 cm -1 are respectively generated by the stretching vibration of CH2 and the stretching vibration of C-H; the characteristic absorption peak around 1455 cm -1 is generated by the asymmetric stretching vibration of C-H; the characteristic absorption peaks at 720 cm -1 , 620 cm -1 are respectively the characteristic absorption peaks of Ti-O and Al-O. The characteristic absorption peaks exist near 1611 cm -1 , 1466 cm -1 . They are respectively the characteristic peaks of aluminum and -COOH and titanium and -COOH. This absorption peak is the characteristic absorption peak of the aluminum-titanium composite coupling agent.

[0038] As described above, the present invention can be preferably realized.

[0039] The embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A synthesis method of an aluminum-titanium bimetallic composite coupling agent, characterized in that It includes the following steps: S1. Synthesize an alcohol-aluminum complex by polymerization reaction using basic aluminum chloride and polyol as raw materials: Completely dissolve basic aluminum chloride in a mixed solution of water and methanol, heat to reflux, continue heating to 100 - 110 °C, add polyol, stir and react. After the reaction ends, filter the solution, distill off the solvent under reduced pressure to obtain a pale yellow solid; dry the solid in an oven at 100 - 110 °C to obtain the required alcohol-aluminum complex; S2. Synthesize an aluminum-titanium bimetallic composite coupling agent using the alcohol-aluminum complex, isopropanol, titanate, fatty carboxylic acid and methanol as raw materials: The mass ratio of titanate to aliphatic carboxylic acid is 1:3 - 1:

12. Add the aliphatic carboxylic acid to isopropanol, stir and dissolve at room temperature. After complete dissolution, gradually add titanate and stir and reflux at 80 - 100 °C; dissolve the alcohol-aluminum complex in methanol by ultrasonic oscillation, add it to the above reaction solution, heat to 100 - 110 °C and continue the reaction. After the reaction ends, distill off the solvent under reduced pressure to obtain a pale yellow solid, that is, the required aluminum-titanium bimetallic composite coupling agent.

2. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, wherein: In step S1, the polyol is any one of polyols with less than 5 carbon atoms.

3. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, characterized in that: In step S2, the titanate is ethyl titanate, isopropyl titanate and / or butyl titanate.

4. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, characterized in that: In step S2, the aliphatic carboxylic acid can be a long-chain carboxylic acid, cycloalkane carboxylic acid and / or unsaturated carboxylic acid with 1 - 18 carbon atoms.

5. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, characterized in that: In step S1, the mass ratio of basic aluminum chloride to water and methanol is 1:1:1.5; the mass ratio of basic aluminum chloride to polyol is 5:

2.

6. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, wherein: In step S2, the reflux reaction temperature is 80 - 90 °C, the methanol dosage is 10 - 20 mL; the mass ratios of titanate to aliphatic carboxylic acid are 1:3, 1:7, 1:9, 1:12 respectively.

7. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, characterized in that: In step S2, the stirring and reflux reaction time at 80 - 100 °C is 1 - 2 hours.

8. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, characterized in that: In step S2, the time for continuing the reaction by heating to 100 - 110 °C is 1 - 2 hours; the ultrasonic oscillation time is 10 - 30 minutes.

9. The synthesis method of the aluminum-titanium bimetallic composite coupling agent according to claim 1, wherein: In step S1, the stirring reaction time is 1 - 2 hours.

10. An aluminum-titanium bimetallic composite coupling agent, characterized in that Obtained by using the synthesis method described in any one of claims 1 - 9.

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