CN110776662A - Preparation method and application of modified brominated butyl rubber porous material - Google Patents

Preparation method and application of modified brominated butyl rubber porous material Download PDF

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CN110776662A
CN110776662A CN201911134510.7A CN201911134510A CN110776662A CN 110776662 A CN110776662 A CN 110776662A CN 201911134510 A CN201911134510 A CN 201911134510A CN 110776662 A CN110776662 A CN 110776662A
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butyl rubber
brominated butyl
porous material
modified brominated
inr
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CN110776662B (en
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欧红香
贡晨霞
郑旭东
黄如君
李凯佳
周东升
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Changzhou University
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Abstract

The invention belongs to the technical field of adsorption material preparation and adsorption separation, and particularly relates to a preparation method and application of a modified brominated butyl rubber porous material. Carbon black CB is used as stable particles, and deionized water is used as a water phase; mixing the modified brominated butyl rubber and petroleum ether, heating and dissolving to obtain an oil phase; after the water phase and the oil phase are mixed, a stable Pickering emulsion is formed; the modified brominated butyl rubber porous material is prepared by using rubber as a base material and using the specific self-crosslinking polymerization capacity of the rubber, and is applied to the adsorption and separation of tetrodotoxin TTX in an aqueous solution. The product has a porous internal structure and good stability, is beneficial to adsorption and separation of target molecules, a large number of adsorption sites are provided by doping and dispersing CB in rubber, and the porous material prepared from the modified brominated butyl rubber has good self-adhesion healing capacity.

Description

Preparation method and application of modified brominated butyl rubber porous material
Technical Field
The invention belongs to the technical field of material preparation and adsorption separation, relates to a preparation method and application of a modified brominated butyl rubber porous material, and particularly relates to a method for preparing a modified brominated butyl rubber porous material doped with nano carbon black particles by a Pickering emulsion template method.
Background
Tetrodotoxin (TTX) belongs to amino perhydro quinazoline compound, is a cage ortho ester alkaloid with molecular formula of C 11H 17N 3O 8. TTX, a typical non-protein neurotoxin, is 1250 times more toxic than cyanide, and binds to receptors on sodium ion channels, resulting in nerve and muscle paralysis, limb weakness, paralysis and the like, and severely poisoned patients die due to central nerve paralysis and respiratory arrest without specific antidotes. TTX can not be decomposed by digestive enzyme in vivo, and neither insolation nor salt pickling can completely destroy its toxicity, and the toxicity can be lost after heating in a pressure cooker for 2 h. TTX has guanidino group as active group, which can specifically bind to sodium ion channel of nerve cell membrane to inhibit Na of nerve cell +The internal flow blocks the conduction of nerve excitation. TTX is used as a specific nerve tool medicine in the neurophysiological research, and has wide application prospects in drug addiction withdrawal, cardiovascular disease treatment, pain relief, local anesthesia and the like.
The blowfish in the southeast coast of China has rich resources and quite complex toxicity distribution. At present, except that low-toxicity parts of individual varieties are used for processing and export, high-toxicity varieties and high-toxicity parts removed in the production process are largely discarded, so that resource waste is caused, and certain environmental pollution is brought. However, TTX itself is expensive, and thus, if TTX in the environment can be adsorbed and separated, it is helpful to realize recycling of waste while reducing environmental risks. Finding a high-performance adsorbing material with high efficiency, low price and strong operability to adsorb and extract TTX in an environmental water sample is particularly important.
The polar resin is mainly used for separating and extracting the TTX adsorbing material at present. The polar resin has higher affinity to TTX toxin, and the TTX toxin can be effectively exchanged on the resin, thereby achieving the purpose of separation and enrichment. However, the existing polar resin does not have the fracture resistance and the self-healing capability.
The prior art for preparing the rubber porous material usually adds a rubber foaming agent, and the shape, the size and the like of a pore structure are difficult to control.
Disclosure of Invention
The invention relates to a porous adsorption material which is prepared by taking modified brominated butyl rubber BIIR as an oil phase, deionized water as a water phase and carbon black particles CB as stable particles, utilizing the self-polymerization capability of the modified brominated butyl rubber at normal temperature and utilizing a water-in-oil emulsion template method, has self-healing capability and stable structure, is used for adsorbing and separating tetrodotoxin TTX of a water sample in the environment, and has better adsorption performance on TTX.
The technical scheme of the invention is as follows:
a preparation method of a modified brominated butyl rubber porous material comprises the following steps:
(1) mixing bromobutyl rubber (BIIR) and butylimidazole in an internal mixer for carrying out a curing experiment, stripping the internal mixer after curing is finished to obtain modified bromobutyl rubber (INR), standing at room temperature, and cooling to normal temperature; the bromine content of BIIR is 0.02 wt% -0.03 wt%, the mass ratio of BIIR to butylimidazole is 25: 1-28: 1, and the curing temperature during banburying is set to be 150 ℃.
(2) Adding the INR obtained in the step (1) into petroleum ether, mixing for later use, and standing at room temperature for more than 4 days to obtain a mixture A; the mass ratio of the petroleum ether to the INR material in the mixture A is 18: 1-22: 1.
(3) Adding Carbon Black (CB) into deionized water, and stirring the mixture into uniformly dispersed suspension by using a high-speed stirrer; the mass ratio of the deionized water to the CB is 150: 1-170: 1.
(4) And (3) heating the mixture A obtained in the step (2) by using a water bath kettle to obtain a uniform turbid mixture B, wherein the heating temperature is set to 65 ℃, and the heating time of the water bath kettle is 1-2 h.
(5) Slowly pouring the suspension obtained in the step (3) into the mixed liquid B obtained in the step (4) while stirring, and continuing for 20-25 min, and uniformly mixing to obtain a mixture C with a flowing form; the mass ratio of INR to CB is 6: 1-9: 1.
(6) And (4) removing excessive water separated by layers in the mixture C obtained in the step (5), pouring into a culture dish, and placing into a 60 ℃ oven for over 24 hours for drying so as to remove other water and petroleum ether.
(7) And (4) washing the material obtained in the step (6) by using deionized water, and then placing the material into a drying oven at 50 ℃ for drying to obtain the modified brominated butyl rubber porous material CB @ INR.
The modified brominated butyl rubber porous material is applied to adsorbing, separating and extracting tetrodotoxin TTX in the environment, and the specific method is carried out according to the following steps:
TTX concentration 10mg/L was prepared and 20mL of TTX solution and 100mg of adsorbent CB @ INR were added to a 50mL Erlenmeyer flask. At 25 ℃, different concentrations (100-800. mu.g.L) were examined -1) And (3) taking the TTX solution after adsorption of the adsorbent on the TTX under different adsorption time (0-720 min), measuring the concentration of the TTX in the solution by using a high performance liquid chromatograph, and calculating the adsorption quantity of the adsorbent according to a formula (1).
Figure BDA0002279233120000031
C oRepresents the initial mass concentration of TTX solution, C tRepresenting the concentration of the TTX solution after a certain time t of adsorption, V being the volume of the TTX solutionW represents the amount of adsorbent used; if the concentration of adsorption equilibrium TTX solution is C eThen Q can be calculated according to the formula t。
The invention has the technical advantages that:
(1) the modified brominated butyl rubber porous material with high adsorption capacity and good self-healing capacity is prepared by taking the modified brominated butyl rubber material as a matrix material and carbon black particles as stable particles and adopting a Pickering emulsion template method, wherein the carbon black also plays a reinforcing role in the rubber, and the carbon black particles are doped in the material, so that the specific surface area of the porous material can be effectively increased, and more adsorption sites are provided. In addition, the carbon black is used as a strong polar material, and the TTX is also a polar molecule, so that the adsorption capacity of the material on the TTX can be enhanced, and a foundation is laid for effective separation/extraction of the TTX in an environmental sample.
(2) The modified brominated butyl rubber has polarity and better adsorption capacity, and the prepared rubber porous material also has anti-cracking performance and excellent self-healing capacity.
(3) The rubber porous material is prepared by adopting a Pickering emulsion template method, and the operation process is simple, controllable and environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope image of a modified brominated butyl rubber porous material; (a) scanning electron micrograph at CB @ INR magnification of 500 times, and (b) scanning electron micrograph at CB @ INR magnification of 30000 times.
Fig. 2 is a self-healing diagram of a modified brominated butyl rubber porous material.
FIG. 3 is an infrared spectrum before and after adsorption of the modified bromobutyl rubber porous material; (a) before and (b) after adsorption of CB @ INR.
FIG. 4 is a graph showing the change of the mass loss rate of the modified brominated butyl rubber porous material after acid-base treatment.
FIG. 525 ℃ is an isotherm representation of TTX adsorption of the modified bromobutyl rubber porous material.
FIG. 6 is a graphical representation of the kinetics of adsorption of TTX by modified bromobutyl rubber porous material.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
25g of brominated butyl rubber and 1g of butylimidazole were weighed out, respectively. And (3) carrying out a curing experiment on the mixture of the components in an internal mixer at a high temperature of 150 ℃ to obtain the butylimidazole modified brominated butyl rubber INR. Weighing 1.6g of modified brominated butyl rubber INR and 30g of petroleum ether, mixing for later use, standing the mixture at room temperature for more than 4 days, heating the mixture for 1 hour by using a water bath kettle, and dissolving INR into uniform mixed liquid by using the petroleum ether at 65 ℃ to obtain solution-state modified brominated butyl rubber INR. 0.16g of CB and 24g of deionized water are weighed and stirred by a high-speed stirrer to form a uniform suspension. And slowly pouring the CB suspension into the INR solution while stirring at the temperature of 65 ℃, and continuously stirring for 20min to obtain a CB @ INR mixed solution. And removing excessive water separated from the mixture material obtained in the last step, pouring the mixture material into a culture dish, and placing the culture dish into a 60 ℃ oven to be dried for more than 24 hours so as to remove other water and petroleum ether. And cleaning the dried material by using deionized water, and drying in an oven at 50 ℃ to obtain the product, namely the modified brominated butyl rubber porous material CB @ INR.
Example 2
26g of brominated butyl rubber and 1g of butylimidazole were weighed out, respectively. And (3) carrying out a curing experiment on the mixture of the components in an internal mixer at a high temperature of 150 ℃ to obtain the butylimidazole modified brominated butyl rubber INR. Weighing 1.5g of modified brominated butyl rubber INR and 30g of petroleum ether, mixing for later use, standing the mixture at room temperature for more than 4 days, heating the mixture for 1.5 hours by using a water bath kettle, and dissolving the INR into uniform mixed liquid by using the petroleum ether at 65 ℃ to obtain the solution-state modified brominated butyl rubber INR. 0.175g of CB and 28g of deionized water were weighed and stirred with a high-speed stirrer to form a uniform suspension. And slowly pouring the CB suspension into the INR solution while stirring at the temperature of 65 ℃, and continuously stirring for 23min to obtain a CB @ INR mixed solution. And removing excessive water separated from the mixture material obtained in the last step, pouring the mixture material into a culture dish, and placing the culture dish into a 60 ℃ oven to be dried for more than 24 hours so as to remove other water and petroleum ether. And cleaning the dried material by using deionized water, and drying in an oven at 50 ℃ to obtain the product, namely the modified brominated butyl rubber porous material CB @ INR.
Example 3
28g of brominated butyl rubber and 1g of butylimidazole were weighed out, respectively. And (3) carrying out a curing experiment on the mixture of the components in an internal mixer at a high temperature of 150 ℃ to obtain the butylimidazole modified brominated butyl rubber INR. Weighing 1.4g of modified brominated butyl rubber INR and 30g of petroleum ether, mixing for later use, standing the mixture at room temperature for more than 4 days, heating the mixture for 1 hour by using a water bath kettle, and dissolving the INR into uniform mixed liquid by using the petroleum ether at 65 ℃ to obtain the solution-state modified brominated butyl rubber INR. 0.135g of CB and 23g of deionized water are weighed and stirred by a high-speed stirrer to form a uniform suspension. And slowly pouring the CB suspension into the INR solution while stirring at the temperature of 65 ℃, and continuously stirring for 25min to obtain a CB @ INR mixed solution. And removing excessive water separated from the mixture material obtained in the last step, pouring the mixture material into a culture dish, and placing the culture dish into a 60 ℃ oven to be dried for more than 24 hours so as to remove other water and petroleum ether. And cleaning the dried material by using deionized water, and drying in an oven at 50 ℃ to obtain the product, namely the modified brominated butyl rubber porous material CB @ INR.
Test example 1: 20mL of the initial concentration were taken and 100. mu.g.L respectively -1，150μg·L -1，200μg·L -1，300μg·L -1，500μg·L -1，800μg·L -1Was added to a 50mL capacity Erlenmeyer flask, and 100mg of the CB @ INR adsorbent material prepared as described above in example 2 was added. Placing the test solution in a shaking table at 25 deg.C, oscillating for 12 hr, filtering with inorganic filter membrane to obtain adsorbent, measuring the concentration of unadsorbed TTX molecules with high performance liquid chromatograph, and calculating the adsorption capacity according to the result.
Test example 2: 20mL of the initial concentration was taken to be 300. mu.g.L -1The TTX solution of (2) was put into a 50 mL-capacity Erlenmeyer flask, 100mg of the CB @ INR adsorbent prepared as described above in example 2 was added, and the test solution was shaken in a shaker at room temperature for 10, 20, 30, 60, 120, 180, 240, 360, 480, 600, and 720 minutes, and then applied to an inorganic filterFiltering the adsorbent, measuring the concentration of the unadsorbed TTX molecules by using a high performance liquid chromatograph, and calculating the adsorption capacity according to the result.
FIGS. 1a and b are scanning electron microscope images of the modified brominated butyl rubber porous material under different proportion conditions, so that the morphology of the CB @ INR material is not uniform, and the graph a shows that the CB @ INR has more micron-sized pore structures with different sizes. In addition to the CB @ INR material in the b diagram exhibiting some nanoscale pore structures, it is also seen that the particles are distributed dispersedly, the particle size can reach nanoscale as shown in the diagram, and it can be seen that the particles are dispersed more uniformly, i.e. carbon black particles doped more uniformly in the rubber are considered.
As can be seen from figure 2, the cut CB @ INR material presses the splice together, and after 24h of healing, the material is firmly adhered together again and does not break again even if being stretched forcibly, which shows that the material has good self-healing capability.
FIG. 3 shows the CB @ INR material at 3420cm -1The absorption peak is relatively wide and strong and corresponds to O-H stretching vibration in the CB @ INR, and the CB @ INR is a porous absorption material and absorbs a large amount of moisture in the air. At 2845 and 2935cm -1The absorption peak at (A) should be C-H stretching vibration. 1340 and 1465cm -1The absorption peak at (a) should be a C-H bending vibration. 1213cm -1The absorption peak at (A) is C-O stretching vibration. The absorption peaks of the infrared spectrogram of CB @ INR before and after absorbing TTX have no obvious change, which shows that the material is more stable, and the structure property change of the material is not influenced in the absorbing process.
FIG. 4 shows the trend of the mass loss rate of the CB @ INR material after treatment with hydrochloric acid and sodium hydroxide. As can be seen from the figure, the material has little mass loss after 20 hours of treatment with acid and alkali solution, and the material has good acid and alkali resistance.
As can be seen from fig. 5, the equilibrium adsorption capacity of the CB @ INR adsorbent material to TTX at 25 ℃ first increases and gradually approaches equilibrium with increasing initial concentration. The two groups of data are fitted by adopting Freundlich and Langmuir isotherm models, the adsorption isotherm of the CB @ INR adsorbing material to the TTX is found to be more consistent with the Langmuir model, and the correlation coefficient of linear fitting is 0.9917.
As can be seen from fig. 6, the adsorption of TTX by the CB @ INR adsorbent material takes about 200min to reach the equilibrium adsorption, which is 96.94% of the equilibrium adsorption. The adsorbent reaches 71.64% of the equilibrium adsorption amount within 60min, and then gradually reaches adsorption equilibrium after adsorption for 120-360 min.

Claims (8)

1. A preparation method of a modified brominated butyl rubber porous material is characterized by comprising the following steps:
(1) mixing bromobutyl rubber (BIIR) and butylimidazole in an internal mixer to carry out a curing experiment, stripping the internal mixer after the curing is finished to obtain modified bromobutyl rubber (INR), standing at room temperature, and cooling to room temperature;
(2) adding the INR obtained in the step (1) into petroleum ether, mixing for later use, and standing at room temperature for more than 4 days to obtain a mixture A;
(3) adding Carbon Black (CB) into deionized water, and stirring the mixture into uniformly dispersed suspension by using a high-speed stirrer;
(4) heating the mixture A obtained in the step (2) by using a water bath kettle to obtain a uniform turbid mixture B,
(5) slowly pouring the suspension obtained in the step (3) into the mixed solution B obtained in the step (4) while stirring, and continuously stirring until the suspension is uniformly mixed to obtain a mixture C with a flowing form;
(6) removing excessive moisture separated by layers in the mixture C obtained in the step (5), pouring the mixture C into a culture dish, and placing the culture dish into a 60 ℃ oven to be dried for more than 24 hours so as to remove other moisture and petroleum ether;
(7) and (4) washing the material obtained in the step (6) by using deionized water, and then placing the material into a drying oven at 50 ℃ for drying to obtain the modified brominated butyl rubber porous material CB @ INR.
2. The preparation method of the modified brominated butyl rubber porous material according to claim 1, wherein the BIIR in the step (1) has a bromine content of 0.02 wt% to 0.03 wt%, the mass ratio of the BIIR to the butylimidazole is 25:1 to 28:1, and the curing temperature during banburying is set to 150 ℃.
3. The preparation method of the modified brominated butyl rubber porous material according to claim 1, wherein the mass ratio of the petroleum ether to the INR material in the mixture A in the step (2) is 18: 1-22: 1.
4. The preparation method of the modified brominated butyl rubber porous material according to claim 1, wherein the mass ratio of the deionized water to the CB in the step (3) is 150: 1-170: 1.
5. The preparation method of the modified brominated butyl rubber porous material according to claim 1, wherein the water bath heating temperature in the step (4) is set to 65 ℃, and the heating time of the water bath is 1-2 h.
6. The preparation method of the modified brominated butyl rubber porous material according to claim 1, wherein the mass ratio of INR to CB in the step (5) is 6: 1-9: 1.
7. The application of the modified brominated butyl rubber porous material prepared by the method according to claim 1, wherein the modified brominated butyl rubber porous material is applied to adsorption separation of tetrodotoxin TTX in an aqueous solution.
8. The application of the modified brominated butyl rubber porous material as claimed in claim 7, wherein the modified brominated butyl rubber porous material is used for adsorbing, separating and extracting tetrodotoxin in the environment, and the specific method is as follows: preparing a TTX solution, adding the TTX solution and an adsorbent CB @ INR into a conical flask, and respectively inspecting the adsorption amount of the adsorbent on the TTX at different concentrations and different adsorption times at 25 ℃.
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CN112250801A (en) * 2020-10-22 2021-01-22 常州大学 Preparation method of flexible shape memory macroporous polymer

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CN112108122A (en) * 2020-08-18 2020-12-22 江苏省农业科学院 Burdock root residue porous adsorption material and preparation method and use method thereof
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CN112250801A (en) * 2020-10-22 2021-01-22 常州大学 Preparation method of flexible shape memory macroporous polymer

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