Cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge

Abstract

The invention discloses a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge, relates to the field of high polymer materials, and provides a novel cycloolefin block copolymer which can be obtained by ring-opening metathesis polymerization of cycloolefin and 5-norbornene-2-carboxylic acid methyl ester under the catalysis of a third-generation Grubbs catalyst. The method is simple in process, and the length of the 5-norbornene-2-carboxylic acid methyl ester block can be accurately regulated, so that the nano shish-kebab structure and the surface performance of the nano shish-kebab structure can be regulated. The process for preparing the nano-hybrid shish-kebab from the cycloolefin block copolymer and the carbon nanotubes is simple in technology, the surface of a rough surface material such as polyurethane sponge can be uniformly covered with the nano-hybrid shish-kebab to form a thin film, super-hydrophobicity can be achieved, and meanwhile the nano-hybrid shish-kebab has oleophylic performance; and the oil-water separator has high separation efficiency and good wear resistance in the oil-water separation process.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge. Background Art

[0002] Sewage prevention and control has become an urgent problem to be solved. Due to the increasing amount of oil and water produced by human daily activities and industrial production, coupled with the frequent oil spills at sea, it has posed a great threat to the marine ecological environment, and oil-water separation has attracted great attention. Superhydrophobic surfaces usually have properties such as bionic anti-adhesion, anti-pollution, water repellency, self-cleaning and oil-water separation. The method of realizing superhydrophobic surfaces includes two steps, namely the construction of rough structures and the chemical modification of low surface energy materials. In nature, the water-repellent surface of superhydrophobic materials such as lotus leaves has a micro-nano structure, and the shish kebab structure, as one of the most fascinating structures in polymer science, is composed of a linear core surrounded by disc-like flake crystals, and also has a micro-nano structure.

[0003] The "nanohybrid shish-kebab (NHSK)" structure is a special form, which is formed by semi-crystalline polymers such as polyethylene (PE), polyvinylidene fluoride and nylon 66 (PA66) on the surface of carbon nanotubes (CNTs) to form periodic disk-like crystals. This special layered nanostructure is completely wrapped on the surface of carbon nanotubes to form a rough NHSK structure, which can promote the interfacial interaction between carbon nanotubes and polymer matrix. There are few reports in the prior art on the use of nanohybrid shish-kebabs to prepare superhydrophobic materials. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the present invention provides a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge.

[0005] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:

[0006] Provided is a method for preparing a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge, comprising the following specific steps:

[0007] A1: The cycloolefin block copolymer is completely dissolved in xylene at 125° C. to obtain a polymer solution;

[0008] A2: ultrasonically dispersing carbon nanotubes in xylene to obtain a CNT / xylene solution;

[0009] A3: Mix the polymer solution and CNT / xylene solution, stir for 30 minutes, immerse the polyurethane sponge in the mixed solution, and crystallize by cooling under ultrasonic dispersion.

[0010] Furthermore, when preparing the polymer solution, the ratio of cycloolefin block copolymer to xylene is 1 mg:5 mL; when preparing the CNT / xylene solution, the ratio of carbon nanotubes to xylene is 3 mg:10 mL; and the mass ratio of cycloolefin block copolymer to carbon nanotubes is 20:9.

[0011] Furthermore, the cycloolefin block copolymer is obtained by ring-opening metathesis polymerization of 5-norbornene-2-carboxylic acid methyl ester and cyclooctene under the catalysis of the third-generation Grubbs catalyst.

[0012] Furthermore, the cycloolefin block copolymer is prepared by the following steps:

[0013] B1: Dissolve the cycloolefin and the third-generation Grubbs catalyst in dichloromethane, place the mixed solution in a dry container preheated to 30°C, and stir the reaction at 30°C for 2h;

[0014] B2: After the stirring reaction is completed, 5-norbornene-2-carboxylic acid methyl ester is added to the reaction system, and the reaction is stirred at 30°C for 2 hours. After the reaction is completed, the precipitate is filtered, washed, and vacuum dried to obtain an unsaturated polymer; the molar ratio of 5-norbornene-2-carboxylic acid methyl ester to the third-generation Grubbs catalyst is 50:1; the molar ratio of cycloolefin to 5-norbornene-2-carboxylic acid methyl ester is 4-18:1;

[0015] B3: The unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol and tripropylamine were dissolved in toluene, and the mixture was heated to reflux at 130° C. under nitrogen atmosphere for 16 h;

[0016] B4: The reflux product is precipitated in an ethanol solution and filtered to obtain a cycloolefin block copolymer.

[0017] Furthermore, the amount ratio of the unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol, tripropylamine solution and toluene is 1 eqv: 5 eqv: 0.1 eqv: 5.5 eqv: 150 mL.

[0018] The present invention also provides a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge prepared by the above-mentioned preparation method.

[0019] The beneficial effects of the present invention are:

[0020] The present invention provides a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge and a preparation method thereof. By loading a cycloolefin copolymer / carbon nanotube hybrid material with low surface energy on the rough sponge structure surface, the prepared modified oil-water separation sponge has super hydrophobic properties, and the sponge has the ability to absorb oil and organic solvents, and can be used as a pollutant adsorption material in sewage prevention and treatment.

[0021] The modified oil-water separation sponge proposed in the present invention can effectively adsorb oil and organic solvents, and can achieve a separation efficiency of 96% to 98% in an oil-water separation test. The cycloolefin copolymer / carbon nanotube hybrid material on the sponge surface has excellent wear resistance, and after repeated oil-water separation, the performance degradation rate is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the infrared spectrum of the block copolymer prepared in Example 1;

[0023] Figure 2 This is a comparison test diagram of the water contact angle of the modified oil-water separation sponge prepared in Example 2;

[0024] Figure 3 This is a comparison chart of the adsorption capacity test of the modified oil-water separation sponge of Example 3 for different oils and solvents;

[0025] Figure 4 This is a comparison chart of the reusability performance test of the modified oil-water separation sponge in Example 3. DETAILED DESCRIPTION

[0026] The specific implementation modes of the present invention are described below so that those skilled in the art can understand the present invention. However, it should be clear that the present invention is not limited to the scope of the specific implementation modes. For those of ordinary skill in the art, as long as various changes are within the spirit and scope of the present invention as defined and determined by the attached claims, these changes are obvious, and all inventions and creations utilizing the concept of the present invention are protected.

[0027] The sources of the raw materials used in the examples are shown in Table 1;

[0028] Table 1

[0029]

[0030] Example 1 Preparation of Cycloolefin Block Copolymer

[0031] The cycloolefin block copolymer is prepared by the following specific steps:

[0032] B1: Dissolve the cycloolefin and the third-generation GrubbS catalyst G3 in dichloromethane, and place the mixed solution in a dry container preheated to 30°C, and stir at 30°C for 2 hours; the molar ratio of 5-norbornene-2-carboxylic acid methyl ester to the third-generation GrubbS catalyst is 50:1;

[0033] B2: After the stirring reaction is completed, 5-norbornene-2-carboxylic acid methyl ester is added to the reaction system, and the reaction is stirred at 30° C. for 2 h. After the reaction is completed, the precipitate is filtered, washed, and vacuum dried to obtain an unsaturated polymer;

[0034] B3: The unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol and tripropylamine were dissolved in toluene, and the mixture was heated to reflux at 130°C in a nitrogen atmosphere for 16 hours; the amount ratio of the unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol, tripropylamine dissolved and toluene was 1eqv: 5eqv: 0.1eqv: 5.5eqv: 150mL;

[0035] B4: The reflux product is precipitated in an ethanol solution and filtered to obtain a cycloolefin block copolymer.

[0036] Cyclic olefin block copolymers with different ratios of cycloolefin COE and 5-norbornene-2-carboxylic acid methyl ester NBMA were prepared respectively, and the molecular weight distribution index of the unsaturated polymer in the preparation process was determined by a Waters-515 gel permeation chromatograph produced by Jinan Saichang Scientific Instrument Co., Ltd., tetrahydrofuran was used as the solvent, the flow rate was 1.0 mL / min, and the measurement was performed at room temperature. The specific ratios and measurement results are shown in Table 2;

[0037] Table 2

[0038]

[0039] As can be seen from Table 2, the conversion rates of cycloolefin block copolymers prepared from different proportions of cycloolefin COE and 5-norbornene-2-carboxylic acid methyl ester NBMA are all higher than 88%, and with the increase of COE block length, the molecular weight of the polymer also increases, and the measured number average molecular weight is basically consistent with the corresponding theoretical molecular weight, indicating that a block structure is formed.

[0040] The infrared spectrum of the prepared cycloolefin block copolymer was measured using an IS10 Fourier transform infrared spectrometer from Thermo Nicolet, USA. The results are as follows: Figure 1 As shown, at 1740cm -1 The peak at is the characteristic peak of C=O in the ester group, indicating that the monomer NBMA successfully participated in the polymerization reaction and obtained a block copolymer. Figure 1It can be seen that block copolymers No. 1, 2, and 3 all showed obvious ester characteristic peaks, and the signals of the ester groups in polymers No. 1 to 3 weakened successively, which indicates that the proportion of NBMA structural units in the copolymer composition decreased. Since the NBMA block was controlled unchanged during feeding, the COE ratio of samples No. 1 to 3 increased successively.

[0041] Example 2 Cyclic olefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge

[0042] According to the results in Example 1, the block copolymer COE900-b-NBMA50 prepared by the No. 3 formula with the best performance in Example 1 was selected for preparing a modified oil-water separation sponge, and the specific steps were as follows: 20 mg of COE900-b-NBMA50 was weighed and dissolved in 100 ml of xylene solution at 125°C. 9 mg of carbon nanotubes CNT were weighed and ultrasonically dispersed in 30 ml of xylene solution for 15 minutes. After the block copolymer was completely dissolved, the dispersed CNT / xylene solution was mixed with the polymer solution;

[0043] The polyurethane sponge was cut into cubes (1.5 cm × 1.5 cm × 1.5 cm), cleaned three times with ethanol ultrasound, and dried in an electric hot air drying oven at 100°C for 2 hours. The pretreated sponge was immersed in the mixed solution for ultrasonic dispersion and cooled to the crystallization temperature, and dried in an oven to obtain a modified oil-water separation sponge.

[0044] The water contact angle test was carried out on the modified oil-water separation sponge, and an unmodified ordinary polyurethane sponge was used as a comparison. The results are as follows: Figure 2 As shown, Figure 2 The left side is the water contact angle test diagram of the modified oil-water separation sponge. Figure 2 The right side is the water contact angle test diagram of polyurethane sponge; Figure 2 It can be seen that after the cycloolefin copolymer / carbon nanotube hybrid material is loaded on the polyurethane sponge, the water contact angle reaches 154.8°, achieving a superhydrophobic effect; while the unmodified polyurethane sponge is only 121.6°.

[0045] Example 3 Performance test of modified oil-water separation sponge

[0046] The modified oil-water separation sponge prepared in Example 2 was immersed in different solvents and greases, and was taken out and weighed after 2 minutes. The mass of the clean sponge in the air was recorded as M0 (g), and then the weighed sample was placed in an organic solvent or grease until adsorption saturation, and was taken out and weighed, and recorded as M1 (g). The adsorption capacity of the sponge was obtained using the following formula.

[0047]

[0048] The adsorption capacity of acetone, toluene, rapeseed oil, silicone oil and chloroform was tested respectively. The test results are as follows Figure 3 As shown in the figure, it can be seen that the adsorption capacity of the prepared modified oil-water separation sponge for oil is 44 to 62 times its own weight, showing a high adsorption capacity for a variety of organic compounds.

[0049] The reusability test was also conducted, using toluene, silicone oil, and chloroform as raw materials, and 15 suction and squeeze cycles were performed to evaluate the cyclic performance of the modified oil-water separation sponge. Figure 4 As shown by Figure 4 It can be seen that after 15 cycles, the adsorption capacity of the modified oil-water separation sponge did not change much, which proved its recyclability and potential for solving the oil spill problem.

Claims

1. A method for preparing a cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge, characterized in that: The specific steps include: A1: The cycloolefin block copolymer is completely dissolved in xylene at 125° C. to obtain a polymer solution; A2: ultrasonically dispersing carbon nanotubes in xylene to obtain a CNT / xylene solution; A3: Mix the polymer solution and CNT / xylene solution, stir for 30 minutes, immerse the polyurethane sponge in the mixed solution, and crystallize by cooling under ultrasonic dispersion.

2. The preparation method according to claim 1, characterized in that: When preparing the polymer solution, the usage ratio of cycloolefin block copolymer to xylene is 1 mg:5 mL; when preparing CNT / xylene solution, the usage ratio of carbon nanotube to xylene is 3 mg:10 mL; and the mass ratio of cycloolefin block copolymer to carbon nanotube is 20:

9.

3. The preparation method according to claim 2, characterized in that: The cycloolefin block copolymer is prepared by ring-opening metathesis polymerization of 5-norbornene-2-carboxylic acid methyl ester and cyclooctene under the catalysis of the third-generation Grubbs catalyst.

4. The preparation method according to claim 3, characterized in that: The cycloolefin block copolymer is prepared by the following steps: B1: Dissolve the cycloolefin and the third-generation Grubbs catalyst in dichloromethane, place the mixed solution in a dry container preheated to 30°C, and stir the reaction at 30°C for 2h; B2: After the stirring reaction is completed, 5-norbornene-2-carboxylic acid methyl ester is added to the reaction system, and the reaction is stirred at 30°C for 2 hours. After the reaction is completed, the precipitate is filtered, washed, and vacuum dried to obtain an unsaturated polymer; the molar ratio of 5-norbornene-2-carboxylic acid methyl ester to the third-generation Grubbs catalyst is 50:1; the molar ratio of cycloolefin to 5-norbornene-2-carboxylic acid methyl ester is 4-18:1; B3: The unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol and tripropylamine were dissolved in toluene, and the mixture was heated to reflux at 130° C. under nitrogen atmosphere for 16 h; B4: The reflux product is precipitated in an ethanol solution and filtered to obtain a cycloolefin block copolymer.

5. The preparation method according to claim 4, characterized in that: The amount ratio of the unsaturated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol, tripropylamine solution and toluene is 1 eqv: 5 eqv: 0.1 eqv: 5.5 eqv: 150 mL.

6. A cycloolefin copolymer / carbon nanotube hybrid material modified oil-water separation sponge prepared by the preparation method of claim 5.

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