CN108864406B - High-mechanical-strength GO/TPU in-situ polymerization method - Google Patents
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Abstract
The invention belongs to the technical field of synthesis of polymer composite materials, and particularly relates to an in-situ polymerization method of GO/TPU with high mechanical strength. The in-situ polymerization method comprises the following specific implementation processes: graphene oxide, polypropylene glycol-4000, toluene diisocyanate and 1, 4-butanediol are used as raw materials, glacial acetic acid and didecyl dimethyl ammonium bromide are adopted to modify the graphene oxide, the modified graphene oxide/polypropylene glycol-4000 blend is formed by combining the modified graphene oxide/polypropylene glycol-4000 blend with the polypropylene glycol-4000, and then the modified graphene oxide/polypropylene glycol-4000 blend is polymerized with the toluene diisocyanate and the 1, 4-butanediol in situ to obtain GO/TPU with high mechanical strength. The GO/TPU material prepared by the method has excellent mechanical strength, and can become a substitute with more excellent performance in the fields of mechanical industry and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of polymer composite materials, and particularly relates to an in-situ polymerization method of GO/TPU with high mechanical strength.
Background
Polymer materials have been widely used in various fields due to their excellent properties, particularly in fields requiring many structural materials such as mechanical industry. The use of high molecular materials with good properties, light weight and convenient processing to replace metals, wood, ceramics and the like has become a popular research in the field of materials nowadays. The high molecular material with high mechanical strength widens the selection range of the material, and the traditional mechanical product gradually finishes the conversion from high consumption, high quality to light weight, corrosion resistance and low cost.
The thermoplastic polyurethane elastomer is also called PU thermoplastic rubber for short, and is a linear block copolymer formed from oligomer polyol soft segment, diisocyanate and chain extender hard segment. The TPU molecule contains a soft segment and a rigid hard segment at the same time, the soft segment enables the TPU to have better elasticity, flexibility and cold resistance, and the hard segment enables the TPU to have higher hardness, elastic modulus and thermal stability. The hydrogen bonds between hard segment molecules and the light crosslinking between macromolecules enable the TPU to have a strong physical crosslinking structure, have strong physical strength, and have good processing performance, so that the TPU has wide application prospects in the fields of automobile parts, machine parts, sports soles, wires and cables, hoses, films, thin plates, fabrics, buildings, food packaging and the like. However, in the field with higher mechanical strength requirement, the mechanical strength of the TPU synthesized by the existing method cannot meet the requirement, so that the synthesis method of the TPU with high mechanical strength becomes a research hotspot.
Graphene is a two-dimensional crystal composed of carbon atoms and having a single atomic layer thickness, and due to its unique two-dimensional conjugated structure, graphene exhibits a number of outstanding physicochemical properties, including a large specific surface area, excellent electrical, thermal, optical and mechanical properties. The method is characterized in that a Hone research group at the university of Columbia in America firstly measures that the fracture strength of graphene is (130 +/-10) GPa and the Young modulus is (1.0 +/-0.1) TPa by using a nano indentation technology, so far, the graphene film is a material with the highest mechanical strength, and the graphene film has a larger deformation range under the action of external force. Many researches have proved that the mechanical strength of the graphene can be greatly improved by uniformly dispersing the graphene into a high polymer material, so that the material with wider application range can be obtained. When the graphene is applied on a large scale, the graphene is easy to agglomerate when added into a high polymer material and cannot be uniformly dispersed, and the graphene cannot be produced in large scale under the existing conditions. The surface of the graphene oxide has more organic groups, so that the graphene oxide can be better dispersed in a high polymer material, and the mechanical strength of the graphene oxide is improved. However, graphene oxide has poor dispersibility in a solvent and is easy to agglomerate, and the graphene oxide needs to be functionally modified by adding the graphene oxide as a modifier in the synthesis process. In the existing research, the performance of modified graphene oxide and TPU is improved by simply and physically blending the modified graphene oxide and TPU after dissolution or melting, so that the performance has a rising threshold value, and the use amount of the graphene oxide is usually required to be larger, so that the cost is increased, and the large-scale industrial application is limited.
The invention adopts glacial acetic acid and didecyl dimethyl ammonium bromide as modifiers of the graphene oxide, and is different from the mechanism of the common method for treating the graphene oxide by acid (such as the method for carrying out carboxylation modification on the graphene oxide by bromoacetic acid). The didecyl dimethyl ammonium bromide and GO are subjected to intercalation reaction so as to improve the dispersibility of the didecyl dimethyl ammonium bromide in a TPU monomer and avoid the agglomeration phenomenon caused by the addition of the modified GO.
Under a proper acid-base environment, the end lipophilicity of the modified graphene oxide enables a system to be converted to a thermodynamic stable state, so that the modified graphene oxide and a TPU monomer polypropylene glycol-4000 are tightly combined through London force, and compared with the conventional method of simply and physically blending the modified graphene oxide and a TPU finished product, which is mostly researched, the method for re-synthesizing the TPU through combining the chemical force between the modified graphene oxide and the monomer can enable the structure of the synthesized functional TPU to be more regular, the distribution of the graphene oxide to be more uniform, and more excellent performance improvement is provided under the condition of less addition amount of the modified graphene oxide.
The high-mechanical-strength GO/TPU is obtained by in-situ polymerization by a prepolymer method, the operation of the in-situ polymerization of the TPU by the prepolymer method is simple and convenient, the equipment process is simple, the side reaction is less, the performance of the prepared product is excellent, and the introduction of harmful substances and impurities in the production process is avoided while the cost is reduced. When the graphene oxide accounts for 0.1% of the TPU by mass, the performance of the TPU is greatly improved compared with that of pure TPU synthesized in situ, wherein the tensile strength is improved by 66.5%, the elongation at break is improved by 60.0%, and the TPU can become a substitute with more excellent performance in the fields of mechanical industry and the like, so that the application range of the TPU is widened.
Disclosure of Invention
The invention aims to provide an in-situ polymerization method of high-mechanical-strength GO/TPU, aiming at the defects that the existing TPU synthesis method cannot obtain TPU with higher mechanical strength under the condition of less addition amount of graphene oxide and the dispersion of the graphene oxide in a high polymer material is poor. The GO/TPU material prepared by the method has excellent mechanical strength, and can become a substitute with more excellent performance in the fields of mechanical industry and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the GO/TPU polymerized raw materials comprise the following components in parts by weight:
0.05-0.1 part of graphene oxide (the mass percentage of the graphene oxide in the TPU);
400060.0 parts of polypropylene glycol;
27.4 parts of toluene diisocyanate;
12.6 parts of 1, 4-butanediol.
The polypropylene glycol-4000 is colorless transparent oily viscous liquid, the hydroxyl value is 26-30 mg KOH/g, the molecular weight is 3700-4300, and the acid value is less than 0.5 mgKOH/g.
The toluene diisocyanate is TDI-80, namely 80% of toluene-2, 4-diisocyanate (2,4-TDI) and 20% of toluene-2, 6-diisocyanate (2,6-TDI), the acidity is below 0.004%, and the toluene diisocyanate is colorless to light yellow transparent liquid with the molecular weight of 174.16.
The 1, 4-butanediol is colorless viscous oily liquid, the molecular weight is 90.12, and the hydroxyl value is 1000-1200 mg KOH/g.
Before the graphene oxide is used, glacial acetic acid and didecyl dimethyl ammonium bromide are sequentially used for modification treatment, wherein the glacial acetic acid is excessive, and the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1.
graphene oxide, polypropylene glycol-4000, toluene diisocyanate and 1, 4-butanediol are used as raw materials, glacial acetic acid and didecyl dimethyl ammonium bromide are adopted to modify the graphene oxide, the modified graphene oxide/polypropylene glycol-4000 blend is formed by combining the modified graphene oxide/polypropylene glycol-4000 blend with the polypropylene glycol-4000, and then the modified graphene oxide/polypropylene glycol-4000 blend is polymerized with the toluene diisocyanate and the 1, 4-butanediol in situ to obtain GO/TPU with high mechanical strength.
The in-situ polymerization method of the GO/TPU with high mechanical strength comprises the following specific steps:
1) preparing graphene oxide: the method is characterized in that crystalline flake graphite is used as a raw material, and an improved Hummers method is adopted to prepare graphene oxide.
2) Preparing modified graphene oxide: pouring glacial acetic acid into graphene oxide, ultrasonically oscillating for 3-4 h, washing the graphene oxide with deionized water to be neutral after the acetic acid naturally volatilizes, dissolving the graphene oxide in the deionized water to obtain a GO solution with the concentration of 2mg/mL, ultrasonically oscillating for 1h, adjusting the pH =9 with 0.1mol/L NaOH solution, adding didecyl dimethyl ammonium bromide, and magnetically stirring for reacting for 2h to obtain the modified graphene oxide suspension.
3) Preparation of modified graphene oxide/polypropylene glycol-4000 blend: slowly adding 30 parts of dehydrated polypropylene glycol-4000 into the modified graphene oxide suspension obtained in the step 2), obtaining a modified graphene oxide/polypropylene glycol-4000 blend under a magnetic stirring state, and freeze-drying to remove water.
4) Adding the residual dewatered polypropylene glycol-4000 and 30 parts of modified graphene oxide/polypropylene glycol-4000 blend into a three-neck flask, placing the three-neck flask in a 70 ℃ constant-temperature magnetic stirrer, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, adding toluene diisocyanate within 15min by using an injector, heating to 80 ℃ for reaction for 1.5h, measuring the content of free isocyanate groups by adopting a di-n-butylamine method, heating to 110 ℃, and adding 1, 4-butanediol under vigorous stirring. And pouring the mixture into a mould when the phenomenon of pole climbing occurs, curing the mixture in a vacuum drying oven at the temperature of 110 ℃ for 10 hours, and extruding and granulating the obtained product to obtain the GO/TPU with high mechanical strength.
Excess glacial acetic acid used in the step 2), the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1.
the invention has the beneficial effects that: according to the invention, glacial acetic acid and didecyl dimethyl ammonium bromide are used as modifiers of graphene oxide, the glacial acetic acid avoids blocking of reaction end groups so as to obtain TPU with higher molecular weight, the didecyl dimethyl ammonium bromide avoids the problems of insufficient reaction degree and easy agglomeration of GO, the mechanical property is greatly improved due to the addition of less modified graphene oxide, when the mass percentage of the graphene oxide in the TPU is up to 0.1%, compared with pure TPU synthesized in situ, the mechanical property is greatly improved, wherein the tensile strength is improved by 66.5%, the elongation at break is improved by 60.0%, and the graphene oxide can become a substitute with better performance in the fields of mechanical industry and the like, so that the application range of the TPU is widened.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
A high-mechanical-strength GO/TPU in-situ polymerization method comprises the following raw materials in parts by weight:
0.05 part of graphene oxide (the mass percentage of the graphene oxide in the TPU);
400060.0 parts of polypropylene glycol;
27.4 parts of toluene diisocyanate;
12.6 parts of 1, 4-butanediol.
The polypropylene glycol-4000 is colorless transparent oily viscous liquid, the hydroxyl value is 26-30 mg KOH/g, the molecular weight is 3700-4300, and the acid value is less than 0.5 mgKOH/g.
The toluene diisocyanate is TDI-80, namely 80% of toluene-2, 4-diisocyanate (2,4-TDI) and 20% of toluene-2, 6-diisocyanate (2,6-TDI), the acidity is below 0.004%, and the toluene diisocyanate is colorless to light yellow transparent liquid with the molecular weight of 174.16.
The 1, 4-butanediol is colorless viscous oily liquid, the molecular weight is 90.12, and the hydroxyl value is 1000-1200 mg KOH/g.
Before the graphene oxide is used, glacial acetic acid and didecyl dimethyl ammonium bromide are sequentially used for modification treatment, wherein the glacial acetic acid is excessive, and the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1.
the in-situ polymerization method of the GO/TPU with high mechanical strength comprises the following specific steps:
1) preparing graphene oxide: preparing graphene oxide by using crystalline flake graphite as a raw material and adopting an improved Hummers method;
2) preparing modified graphene oxide: pouring glacial acetic acid into graphene oxide, ultrasonically oscillating for 3-4 h, washing the graphene oxide with deionized water to be neutral after the acetic acid naturally volatilizes, dissolving the graphene oxide in the deionized water to obtain a GO solution with the concentration of 2mg/mL, ultrasonically oscillating for 1h, adjusting the pH =9 with 0.1mol/L NaOH solution, adding didecyl dimethyl ammonium bromide, and magnetically stirring for reacting for 2h to obtain a modified graphene oxide suspension;
3) preparation of modified graphene oxide/polypropylene glycol-4000 blend: slowly adding 30 parts of dehydrated polypropylene glycol-4000 into the modified graphene oxide suspension obtained in the step 2), obtaining a modified graphene oxide/polypropylene glycol-4000 blend under a magnetic stirring state, and freeze-drying to remove water;
4) adding the residual dewatered polypropylene glycol-4000 and 30 parts of modified graphene oxide/polypropylene glycol-4000 blend into a three-neck flask, placing the three-neck flask in a constant-temperature magnetic stirrer at 70 ℃, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, adding toluene diisocyanate within 15min by using an injector, heating to 80 ℃ to react for 1.5h, measuring the content of free isocyanate groups by adopting a di-n-butylamine method to be unchanged, heating to 110 ℃, adding 1, 4-butanediol under vigorous stirring, pouring into a mold after the phenomenon of 'rod climbing' occurs, aging in a vacuum drying oven at 110 ℃ for 10h, and extruding and granulating the obtained product to obtain the high-mechanical strength GO/TPU.
Example 2
A high-mechanical-strength GO/TPU in-situ polymerization method comprises the following raw materials in parts by weight:
0.08 part of graphene oxide (the mass percentage of the graphene oxide in the TPU);
400060.0 parts of polypropylene glycol;
27.4 parts of toluene diisocyanate;
12.6 parts of 1, 4-butanediol.
The polypropylene glycol-4000 is colorless transparent oily viscous liquid, the hydroxyl value is 26-30 mg KOH/g, the molecular weight is 3700-4300, and the acid value is less than 0.5 mgKOH/g.
The toluene diisocyanate is TDI-80, namely 80% of toluene-2, 4-diisocyanate (2,4-TDI) and 20% of toluene-2, 6-diisocyanate (2,6-TDI), the acidity is below 0.004%, and the toluene diisocyanate is colorless to light yellow transparent liquid with the molecular weight of 174.16.
The 1, 4-butanediol is colorless viscous oily liquid, the molecular weight is 90.12, and the hydroxyl value is 1000-1200 mg KOH/g.
Before the graphene oxide is used, glacial acetic acid and didecyl dimethyl ammonium bromide are sequentially used for modification treatment, wherein the glacial acetic acid is excessive, and the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1.
the in-situ polymerization method of the GO/TPU with high mechanical strength comprises the following specific steps:
1) preparing graphene oxide: preparing graphene oxide by using crystalline flake graphite as a raw material and adopting an improved Hummers method;
2) preparing modified graphene oxide: pouring glacial acetic acid into graphene oxide, ultrasonically oscillating for 3-4 h, washing the graphene oxide with deionized water to be neutral after the acetic acid naturally volatilizes, dissolving the graphene oxide in the deionized water to obtain a GO solution with the concentration of 2mg/mL, ultrasonically oscillating for 1h, adjusting the pH =9 with 0.1mol/L NaOH solution, adding didecyl dimethyl ammonium bromide, and magnetically stirring for reacting for 2h to obtain a modified graphene oxide suspension;
3) preparation of modified graphene oxide/polypropylene glycol-4000 blend: slowly adding 30 parts of dehydrated polypropylene glycol-4000 into the modified graphene oxide suspension obtained in the step 2), obtaining a modified graphene oxide/polypropylene glycol-4000 blend under a magnetic stirring state, and freeze-drying to remove water;
4) adding the residual dewatered polypropylene glycol-4000 and 30 parts of modified graphene oxide/polypropylene glycol-4000 blend into a three-neck flask, placing the three-neck flask in a 70 ℃ constant-temperature magnetic stirrer, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, adding toluene diisocyanate within 15min by using an injector, heating to 80 ℃ for reaction for 1.5h, measuring the content of free isocyanate groups by adopting a di-n-butylamine method, heating to 110 ℃, and adding 1, 4-butanediol under vigorous stirring. And pouring the mixture into a mould when the phenomenon of pole climbing occurs, curing the mixture in a vacuum drying oven at the temperature of 110 ℃ for 10 hours, and extruding and granulating the obtained product to obtain the GO/TPU with high mechanical strength.
Example 3
A high-mechanical-strength GO/TPU in-situ polymerization method comprises the following raw materials in parts by weight:
0.1 part of graphene oxide (the mass percentage of the graphene oxide in the TPU);
400060.0 parts of polypropylene glycol;
27.4 parts of toluene diisocyanate;
12.6 parts of 1, 4-butanediol.
The polypropylene glycol-4000 is colorless transparent oily viscous liquid, the hydroxyl value is 26-30 mg KOH/g, the molecular weight is 3700-4300, and the acid value is less than 0.5 mgKOH/g.
The toluene diisocyanate is TDI-80, namely 80% of toluene-2, 4-diisocyanate (2,4-TDI) and 20% of toluene-2, 6-diisocyanate (2,6-TDI), the acidity is below 0.004%, and the toluene diisocyanate is colorless to light yellow transparent liquid with the molecular weight of 174.16.
The 1, 4-butanediol is colorless viscous oily liquid, the molecular weight is 90.12, and the hydroxyl value is 1000-1200 mg KOH/g.
Before the graphene oxide is used, glacial acetic acid and didecyl dimethyl ammonium bromide are sequentially used for modification treatment, wherein the glacial acetic acid is excessive, and the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1.
the in-situ polymerization method of the GO/TPU with high mechanical strength comprises the following specific steps:
1) preparing graphene oxide: preparing graphene oxide by using crystalline flake graphite as a raw material and adopting an improved Hummers method;
2) preparing modified graphene oxide: pouring glacial acetic acid into graphene oxide, ultrasonically oscillating for 3-4 h, washing the graphene oxide with deionized water to be neutral after the acetic acid naturally volatilizes, dissolving the graphene oxide in the deionized water to obtain a GO solution with the concentration of 2mg/mL, ultrasonically oscillating for 1h, adjusting the pH =9 with 0.1mol/L NaOH solution, adding didecyl dimethyl ammonium bromide, and magnetically stirring for reacting for 2h to obtain a modified graphene oxide suspension;
3) preparation of modified graphene oxide/polypropylene glycol-4000 blend: slowly adding 30 parts of dehydrated polypropylene glycol-4000 into the modified graphene oxide suspension obtained in the step 2), obtaining a modified graphene oxide/polypropylene glycol-4000 blend under a magnetic stirring state, and freeze-drying to remove water;
4) adding the residual dewatered polypropylene glycol-4000 and 30 parts of modified graphene oxide/polypropylene glycol-4000 blend into a three-neck flask, placing the three-neck flask in a 70 ℃ constant-temperature magnetic stirrer, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, adding toluene diisocyanate within 15min by using an injector, heating to 80 ℃ for reaction for 1.5h, measuring the content of free isocyanate groups by adopting a di-n-butylamine method, heating to 110 ℃, and adding 1, 4-butanediol under vigorous stirring. And pouring the mixture into a mould when the phenomenon of pole climbing occurs, curing the mixture in a vacuum drying oven at the temperature of 110 ℃ for 10 hours, and extruding and granulating the obtained product to obtain the GO/TPU with high mechanical strength.
The GO/TPU's obtained in examples 1-3 were compared to the in situ polymerized pure TPU and the results are shown in Table 1.
TABLE 1 sample Performance test
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A high mechanical strength GO/TPU in-situ polymerization method is characterized in that: the GO/TPU comprises the following raw materials in parts by weight: 0.05-0.1 part of graphene oxide, 60.0 parts of polypropylene glycol-4000, 27.4 parts of toluene diisocyanate and 12.6 parts of 1, 4-butanediol;
the toluene diisocyanate is TDI-80;
before the graphene oxide is used, glacial acetic acid and didecyl dimethyl ammonium bromide are sequentially used for treatment, wherein the glacial acetic acid is excessive, and the mass ratio of the graphene oxide to the didecyl dimethyl ammonium bromide is 3: 1;
the method specifically comprises the following steps:
1) preparing graphene oxide: preparing graphene oxide by using crystalline flake graphite as a raw material and adopting an improved Hummers method;
2) preparing modified graphene oxide: pouring glacial acetic acid into graphene oxide, ultrasonically oscillating for 3-4 h, washing the graphene oxide with deionized water to be neutral after the acetic acid naturally volatilizes, dissolving the graphene oxide in the deionized water, controlling the concentration to be 2mg/mL, ultrasonically oscillating for 1h, adjusting the pH of the solution to be =9 by using 0.1mol/L NaOH solution, adding didecyl dimethyl ammonium bromide, and magnetically stirring for reacting for 2h to obtain a modified graphene oxide suspension;
3) preparation of modified graphene oxide/polypropylene glycol-4000 blend: slowly adding 30 parts of dehydrated polypropylene glycol-4000 into the modified graphene oxide suspension obtained in the step 2), obtaining a modified graphene oxide/polypropylene glycol-4000 blend under a magnetic stirring state, and freeze-drying to remove water;
4) adding the rest of the dewatered polypropylene glycol-4000 and modified graphene oxide/polypropylene glycol-4000 blend into a three-neck flask, placing the three-neck flask into a constant-temperature magnetic stirrer at 70 ℃, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, completely adding toluene diisocyanate within 15min by using an injector, heating to 80 ℃ to react for 1.5h, measuring the content of free isocyanate groups by adopting a di-n-butylamine method, heating to 110 ℃, adding 1, 4-butanediol under vigorous stirring, pouring into a mould when a pole climbing phenomenon occurs, aging in a vacuum drying oven at 110 ℃ for 10h, and extruding and granulating the obtained product to obtain the high-mechanical strength/GO.
2. The in-situ polymerization method of high mechanical strength GO/TPU according to claim 1, characterized in that: modifying graphene oxide by adopting glacial acetic acid and didecyl dimethyl ammonium bromide, combining the modified graphene oxide with polypropylene glycol-4000 to form a modified graphene oxide/polypropylene glycol-4000 blend, and carrying out in-situ polymerization on the modified graphene oxide/polypropylene glycol-4000 blend with toluene diisocyanate and 1, 4-butanediol to obtain GO/TPU with high mechanical strength.
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