CN112970773A - Preparation method and device of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant - Google Patents
Preparation method and device of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-efficiency environment-friendly maleic anhydride grafted polyguanidine disinfectant, wherein an organic-inorganic mixed solvent is adopted to carry out ultrasonic-assisted dissolution on poly-guanidine hexamethylene hydrochloride before grafting, and a grafting product is subjected to rotary evaporation-sedimentation combined impurity removal purification to prepare the high-purity maleic anhydride grafted polyguanidine disinfectant; the organic-inorganic mixed solvent is a mixed solvent of absolute ethyl alcohol and water; the ultrasonic-assisted dissolution is carried out at the ultrasonic intensity of 25-30W/cm3, the ultrasonic frequency of 30-50KHz and the action time of 10-30 min. The invention adopts the solution formed by mixing water and absolute ethyl alcohol according to the volume ratio of 1:2 as the solvent to replace the original solvent dimethyl sulfoxide with higher boiling point, thereby achieving the purpose of dissolving the disinfectant more quickly, removing the residual solvent in the product after the reaction is finished and shortening the reaction time.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method and a preparation device of a maleic anhydride grafted polyguanidine disinfectant.
Background
In recent years, guanidine disinfectants are widely used in daily life. The polyhexamethylene monoguanidine has bactericidal performance, particularly has stronger bactericidal activity, is easy to dissolve in water, is colorless, tasteless and nontoxic in aqueous solution, is green, environment-friendly and pollution-free, and is widely applied to industry, medical use and daily life. Maleic anhydride contains unsaturated double bonds and can also be used as a fungicide. Therefore, the maleic anhydride is bonded to the poly-guanidine-hexamethylenehydrochloride to achieve the purpose of chemical grafting modification of the guanidine polymer, so that the product has better thermal stability, the problems of loss of the antibacterial agent and the like are solved, and the product has better effect of inhibiting escherichia coli.
Yang Guifu and the like (synthesis and characterization of functional oligomer guanidine salt cationic monomer material. novel chemical materials 2015, 43(2), 129-131.) adopt dimethyl sulfoxide (DMSO) as a reaction solvent, and maleic anhydride is grafted to poly-guanidine hexamethylene hydrochloride with guanidine groups, which is synthesized by a melt polycondensation method, so as to prepare the product. The solvent used in the method is dimethyl sulfoxide which has high polarity, is miscible with water, can be dissolved in most organic solvents such as ethanol, acetone and the like, and is called as a universal solvent. But the boiling point is 189 ℃, the volatilization is difficult, and the high boiling point enables a part of the product to be remained in the product after the reaction as a solvent is finished, so that the purification is difficult to be completed, the detection of the product is influenced, and the antibacterial performance of the product is not obvious.
On a preparation device, in the process of producing the maleic anhydride grafted polyguanidine disinfectant, because the viscosity of a reaction liquid obtained after mixing of raw materials is high, in the reaction process, gas in the reaction liquid needs to be discharged out of a reaction kettle, generally, an exhaust pipe is arranged at the upper part of the reaction kettle, the gas rises and is discharged through the exhaust pipe, and because the temperature at the exhaust pipe is not high, the inner wall of the exhaust pipe generates a crystallization phenomenon and blocks the exhaust pipe due to long-time exhaust. And the lower part of the reaction kettle has low temperature, and the mixed liquid is easy to solidify into solid, so that the discharging is difficult.
Disclosure of Invention
The invention aims to provide a preparation method and a device of a maleic anhydride grafted polyguanidine disinfectant, which are efficient and environment-friendly.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
Preparation of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectantThe method comprises the steps of carrying out ultrasonic-assisted dissolution on polyhexamethylene guanidine hydrochloride by adopting an organic-inorganic mixed solvent before grafting, and carrying out rotary evaporation-sedimentation combined impurity removal purification on a grafting product to efficiently prepare the high-purity maleic anhydride grafted polyguanidine disinfectant; the organic-inorganic mixed solvent is a mixed solvent of absolute ethyl alcohol and water; the ultrasonic intensity of the ultrasonic-assisted dissolution is set to be 25-30W/cm3Ultrasonic frequency is 30-50KHz, and action time is 10-30 min; the row rotary evaporation-sedimentation combined impurity removal and purification operation is carried out by firstly carrying out rotary evaporation under the following process parameters: rotary steaming at 40-45 deg.C under-0.090 Mpa to-0.1005 Mpa for 15-25min, adding acetone, settling, decanting to remove supernatant, and repeating the operation for 2-4 times.
As a preferred technical solution of the present invention, the organic-inorganic mixed solvent is a mixed solvent of absolute ethyl alcohol and water; the ultrasonic intensity of the ultrasonic-assisted dissolution setting is 27.5W/cm3Ultrasonic frequency is 40KHz, and action time is 20 min; the rotary evaporation-sedimentation combined impurity removal and purification operation is carried out by firstly carrying out rotary evaporation under the following process parameters: rotary steaming at 42 deg.C under-0.095 Mpa for 20min, adding acetone, settling, decanting to remove supernatant, and repeating the operation 3 times.
In a preferable embodiment of the present invention, in the mixed solvent of absolute ethyl alcohol and water, the volume ratio of absolute ethyl alcohol to water is (1.5-2.5): 1.
In a preferred embodiment of the present invention, in the mixed solvent of absolute ethyl alcohol and water, the volume ratio of absolute ethyl alcohol to water is 2: 1.
As a preferred technical scheme of the invention, the method firstly prepares the poly-guanidine-hexamethylenehydrochloride before grafting, uses 1, 6-hexamethylene diamine and guanidine hydrochloride as initial raw materials and polyethylene glycol as an initiator, and synthesizes the disinfectant poly-guanidine-hexamethylenehydrochloride by adopting a high-temperature thermal polycondensation reaction.
In a preferred embodiment of the present invention, the method first performs the preparation of polyhexamethylene guanidine hydrochloride before grafting, and 1, 6-hexamethylenediamine and guanidine hydrochloride are mixed in a ratio of 1: 1, adding the mixture into a dry reaction container, introducing nitrogen by using polyethylene glycol as an initiator, heating and stirring the mixture from room temperature under the protection of nitrogen, and absorbing tail gas; heating the mixture to 60-80 ℃ from room temperature, keeping the temperature for 20min at every 10 ℃ rise within the temperature range of 60-120 ℃, keeping the temperature for 30min-60min at the temperature of 130 ℃, keeping the temperature for 20min-30min at every 10 ℃ rise when the temperature rises from 130 ℃ to 170-180 ℃, and continuing to perform constant temperature reaction for 4-7 h to complete the polymerization reaction.
In a preferred embodiment of the present invention, the method first performs the preparation of polyhexamethylene guanidine hydrochloride before grafting, and 1, 6-hexamethylenediamine and guanidine hydrochloride are mixed in a ratio of 1: 1, adding the mixture into a dry reaction container, introducing nitrogen by using polyethylene glycol as an initiator, and heating and stirring from room temperature under the protection of nitrogen; and keeping the temperature for 30-60 min every time the temperature is increased by 30-50 ℃ within the temperature range of 60-160 ℃ until the temperature is increased to 170-180 ℃, and continuing to perform constant temperature reaction for 4-7 h to finish the polymerization reaction.
As a preferred technical scheme, after the poly-guanidine-hexamethylenehydrochloride is subjected to ultrasonic-assisted dissolution, maleic anhydride is added under the conditions of nitrogen protection and constant temperature for grafting reaction, so that a crude grafting product of maleic anhydride grafted poly-guanidine is obtained.
As a preferable technical scheme of the invention, after the poly-hexamethylene guanidine hydrochloride is subjected to ultrasonic-assisted dissolution, the method comprises the following steps of mixing maleic anhydride and a disinfectant according to a molar ratio of 1.2:1, adding maleic anhydride to completely dissolve the maleic anhydride to form a homogeneous system; then adding the mixture into a reaction vessel, introducing nitrogen, and reacting for 13 hours under the protection of nitrogen by heating in a water bath at 45 ℃ and magnetic stirring.
A reaction kettle for preparing a maleic anhydride grafted polyguanidine disinfectant comprises an exhaust pipe constructed at the upper part of the reaction kettle, wherein a first material scraping part used for scraping crystal on the inner wall of the exhaust pipe is installed on the exhaust pipe, a material discharging mechanism extending into the conveying pipe is installed on a conveying pipe at the lower end of the reaction kettle, and a second material scraping part used for scraping material on the bottom wall of the reaction kettle is constructed at the upper end of the material discharging mechanism; the reaction kettle comprises a vertically arranged cylindrical kettle body, the upper end and the lower end of the kettle body are respectively detachably connected with an end cover and a blanking hopper, and the edge of the second scraping piece is close to the inner wall of the blanking hopper; the end cover is of an upward protruding arc-shaped structure, a feeding pipe communicated with the interior of the reaction kettle is constructed at the top of the end cover, and the exhaust pipe is constructed on the end cover; a plurality of fixing lugs are arranged on the outer wall of the lower part of the kettle body at intervals along the circumferential direction of the kettle body, and the kettle body is fixed on the bracket through the fixing lugs; the outer wall of the discharging hopper is sleeved with an electric heating wire spirally extending along the axis of the discharging hopper; the first scraping piece comprises a fixing ring arranged at the end part of the exhaust pipe, a plurality of scraping pieces are formed on the fixing ring at intervals along the circumferential direction of the fixing ring, and each scraping piece is respectively contacted with the inner wall of the exhaust pipe; the scraping sheet is an elastic sheet made of a metal material, the scraping sheet is elastically expanded on the inner wall of the exhaust pipe, a mounting bar extending outwards along the radial direction of the fixing ring is constructed on the fixing ring, and a hand lever is constructed on the mounting bar; the discharging mechanism comprises a rotating shaft coaxially connected with an output shaft of a forward and reverse rotating motor, blades spirally extending along the axis of the rotating shaft are constructed on the rotating shaft, both the rotating shaft and the blades extend into the conveying pipe from the lower end of the conveying pipe, and a discharging port is constructed at the lower part of the conveying pipe; the rotating shaft extends to the upper part of the reaction kettle from the lower end of the conveying pipe along the vertical direction, the second scraping part is assembled on the rotating shaft and positioned on the upper part of the blade, and a first stirring part and a second stirring part are vertically and upwardly assembled on the rotating shaft above the second scraping part at intervals; the first stirring piece comprises a plurality of first mounting rods which are uniformly arranged along the axial direction of the rotating shaft, each first mounting rod extends outwards along the radial direction of the rotating shaft, a plurality of first stirring rods are constructed on each first mounting rod at intervals along the length direction of the first mounting rod, and each first stirring rod extends upwards in the vertical direction; the second stirring piece comprises a plurality of second mounting rods which are evenly arranged along the axial direction of the rotating shaft, each second mounting rod extends outwards along the radial direction of the rotating shaft, a plurality of second stirring rods are constructed on each second mounting rod along the length direction of the second mounting rod at intervals, each second stirring rod extends downwards vertically, and the motion trail of each second stirring rod is located between the motion trails of two adjacent first stirring rods.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the invention adopts the solution formed by mixing water and absolute ethyl alcohol according to the volume ratio of 1:2 as the solvent to replace the original solvent dimethyl sulfoxide with higher boiling point, thereby not only achieving the purpose of enabling the disinfectant to be dissolved more quickly, but also enabling the residual solvent in the product to be removed more easily after the reaction is finished, and shortening the reaction time; adding magnetons into the flask for magnetic stirring, so that the stirring speed is regulated stably and conveniently; the added step of rotary evaporation of the crude grafting product can ensure that the solvent in the product is heated and removed under the negative pressure state, further purify the product and improve the yield of the product. And the detection result of the product obtained by the invention shows that the product has good antibacterial effect.
When crystals are attached to the inner wall of the exhaust pipe to influence exhaust, an operator scrapes off the crystals on the inner wall of the exhaust pipe by controlling the first scraping part, so that the exhaust pipe is cleaned; after cleaning, an operator can disassemble the first scraping piece, remove crystals on the first scraping piece and install the first scraping piece on the exhaust pipe; arrange material mechanism and install in the conveyer pipe, arrange material mechanism and improve reation kettle in the material exhaust in-process, the drive second is scraped the material and is scraped the material to the reation kettle diapire, and then has avoided the material deposit on the diapire and condense or appear the crystallization, avoids blockking up the bin outlet, avoids the phenomenon emergence that the crystallization was gathered simultaneously.
Drawings
FIG. 1 shows PHGC as a product obtained in the preparation step of polyhexamethylene guanidine hydrochloride (PHGC).
FIG. 2 is a photograph of a sample which is not rotovapped after the completion of the crude grafting reaction of maleic anhydride and a polyguanidine disinfectant.
FIG. 3 is a photograph A showing the results of detection of Escherichia coli.
FIG. 4 is a photograph B showing the results of detection of Escherichia coli.
FIG. 5 is a photograph of a sample without acetone precipitation after rotary evaporation in the purification step of a crude graft product of a maleic anhydride-grafted polyguanidine disinfectant.
FIG. 6 is a photograph of a sample precipitated by adding acetone in the purification step of a crude graft product of a maleic anhydride-grafted polyguanidine disinfectant.
Fig. 7 is a picture of a sample after vacuum drying in the purification step of a crude graft product of a maleic anhydride-grafted polyguanidine disinfectant.
FIG. 8 shows the reaction scheme for preparing poly-guanidine-hexamethylenehydrochloride (PHGC) in the upper formula and the reaction scheme for grafting maleic anhydride with poly-guanidine-hexamethylenehydrochloride in the lower formula.
FIG. 9 is a schematic structural view of an embodiment of a manufacturing apparatus.
FIG. 10 is a partial structural sectional view of an embodiment of a manufacturing apparatus.
FIG. 11 is a schematic view of a reactor in an embodiment of a preparation device after disassembly.
FIG. 12 is a schematic structural view of a scraping mechanism, a second scraping member, a first stirring member and a second stirring member in an embodiment of a manufacturing apparatus.
FIG. 13 is a schematic structural view of a first scraper member of an embodiment of a manufacturing apparatus.
Labeling components: 100-kettle body, 101-fixing lug, 102-end cover, 103-feeding pipe, 104-exhaust pipe, 105-discharging hopper, 106-conveying pipe, 107-discharging port, 200-positive and negative rotation motor, 201-rotating shaft, 202-second mounting rod, 203-second stirring rod, 204-first connecting sleeve, 205-first mounting rod, 206-first stirring rod, 207-second connecting sleeve, 208-second scraping piece, 209-third connecting sleeve, 210-blade, 211-cover plate, 300-first scraping piece, 301-fixing ring, 302-scraping piece, 303-mounting strip, 304-hand rod and 400-electric heating wire.
Detailed Description
The following examples illustrate the invention in detail. The raw materials and various devices used in the invention are conventional commercially available products, and can be directly obtained by market purchase.
In the following description of embodiments, for purposes of explanation and not limitation, specific details are set forth, such as particular system structures, techniques, etc. in order to provide a thorough understanding of the embodiments of the present application. It will be apparent, however, to one skilled in the art that the present application may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present application with unnecessary detail.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It should also be understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
Furthermore, in the description of the present application and the appended claims, the terms "first," "second," "third," and the like are used for distinguishing between descriptions and not necessarily for describing or implying relative importance.
Reference throughout this specification to "one embodiment" or "some embodiments," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in one or more embodiments of the present application. Thus, appearances of the phrases "in one embodiment," "in some embodiments," "in other embodiments," or the like, in various places throughout this specification are not necessarily all referring to the same embodiment, but rather "one or more but not all embodiments" unless specifically stated otherwise. The terms "comprising," "including," "having," and variations thereof mean "including, but not limited to," unless expressly specified otherwise.
Example 1 Synthesis of Polyhexamethyleneguanidine hydrochloride
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating the mixture to 60 ℃ from room temperature, keeping the temperature at 60-120 ℃ for 20min at 10 ℃ per liter, keeping the temperature at 130 ℃ for 1h, keeping the temperature at 130-170 ℃ at 10 ℃ per liter for 20min-30min, keeping the temperature at 180 ℃ for 4h, and finishing the polymerization reaction to obtain a white solid product.
Example 2 Synthesis of polyhexamethylene guanidine hydrochloride
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating the mixture to 60 ℃ from room temperature, keeping the temperature at 60-120 ℃ for 20min at 10 ℃ per liter, keeping the temperature at 130 ℃ for 1h, keeping the temperature at 130-170 ℃ at 10 ℃ per liter for 20min-30min, keeping the temperature at 180 ℃ for 5h, and finishing the polymerization reaction to obtain a white solid product.
Example 3 Synthesis of polyhexamethylene guanidine hydrochloride (III)
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating the mixture to 60 ℃ from room temperature, keeping the temperature at 60-120 ℃ for 20min at 10 ℃ per liter, keeping the temperature at 130 ℃ for 1h, keeping the temperature at 130-170 ℃ at 10 ℃ per liter for 20min-30min, keeping the temperature at 180 ℃ for 6h, and finishing the polymerization reaction to obtain a white solid product.
Example 4 Synthesis of polyhexamethylene guanidine hydrochloride (IV)
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating to 80 ℃ from room temperature, keeping the temperature at 80-120 ℃ for 20min at 10 ℃ per liter, keeping the temperature at 130 ℃ for 1h, keeping the temperature at 130-170 ℃ per liter for 20min-30min, keeping the temperature at 180 ℃ for 6h, and finishing the polymerization reaction to obtain a white solid product.
Example 5 Synthesis of polyhexamethylene guanidine hydrochloride (V)
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating the mixture from room temperature to 60 ℃, then heating the mixture to 130 ℃ and 160 ℃, preserving heat for 1h, preserving heat for 6h at 180 ℃, and finishing polymerization reaction to obtain a white solid product.
Example 6 Synthesis of polyhexamethylene guanidine hydrochloride (Hexa)
Adding 1, 6-hexamethylene diamine 1mol and guanidine hydrochloride into a dry 250mL four-neck flask, firstly pumping away more air in the flask by using a water pump, then introducing nitrogen, heating and stirring under the protection of nitrogen, and performing tail gas absorption and removal. Heating to 80 ℃ from room temperature, then heating to 130 ℃ and 160 ℃, preserving heat for 1h, preserving heat for 6h at 180 ℃, and finishing polymerization reaction to obtain a white solid product.
Example 7 maleic anhydride and Polyguanidine disinfectant solubility test
Dissolving maleic anhydride in water, absolute ethyl alcohol and acetone, wherein the maleic anhydride can be dissolved; and dissolving the synthesized polyhexamethylene guanidine hydrochloride in absolute ethyl alcohol and acetone to obtain the polyhexamethylene guanidine hydrochloride which is insoluble in absolute ethyl alcohol and acetone.
Example 8 Synthesis of maleic anhydride and Polyguanidine disinfectant
Mixing water and absolute ethyl alcohol according to the proportion of 1:2 to prepare 30ml of mixed solvent, adding 3g of synthetic disinfectant, dissolving the disinfectant in ultrasonic waves, and adding 0.071g of maleic anhydride according to the molar ratio of 1.2:1 to dissolve the disinfectant to form a homogeneous system. And finally, adding the mixed solution into a four-neck flask, introducing nitrogen, and reacting for 9 hours under the protection of nitrogen by heating in a water bath at 45 ℃ and in a magnetic stirring manner.
Example 9 Synthesis of maleic anhydride and Polyguanidine disinfectant
Mixing water and absolute ethyl alcohol according to the proportion of 1:2 to prepare 15ml of mixed solvent, adding 3g of synthetic disinfectant, dissolving the disinfectant in ultrasonic waves, and adding 0.071g of maleic anhydride to dissolve to form a homogeneous system. And finally, adding the mixed solution into a four-neck flask, introducing nitrogen, and reacting for 10 hours under the protection of nitrogen by heating in a water bath at 45 ℃ and in a magnetic stirring manner.
Example 10 Synthesis of maleic anhydride and Polyguanidine disinfectant
Mixing water and absolute ethyl alcohol according to the proportion of 1:2 to prepare 15ml of mixed solvent, adding 3g of synthetic disinfectant, dissolving the disinfectant in ultrasonic waves, and adding 0.071g of maleic anhydride to dissolve to form a homogeneous system. And finally, adding the mixed solution into a four-neck flask, introducing nitrogen, and reacting for 13 hours under the protection of nitrogen by heating in a water bath at 45 ℃ and in a magnetic stirring manner.
EXAMPLE 11 purification of maleic anhydride grafted polyguanidine disinfectant product
And (3) carrying out rotary evaporation on the light yellow liquid obtained after the reaction is finished at 45 ℃ under-0.095 Mpa by using a rotary evaporator for 20min, adding acetone for sedimentation, removing a supernatant by decantation, repeating the operation for three times, and finally carrying out vacuum drying at 25 ℃ for 12 h.
Example 12 purification of maleic anhydride grafted polyguanidine disinfectant product
And (3) carrying out rotary evaporation on the light yellow liquid obtained after the reaction is finished at 42 ℃ under the pressure of-0.095 Mpa for 20min by using a rotary evaporator, adding acetone for sedimentation, removing a supernatant by decantation, repeating the operation for three times, and finally carrying out vacuum drying at room temperature for 12 h.
Example 13 antimicrobial Property measurement of graft product
And (3) testing the bacteriostatic effect of the grafted product on escherichia coli: the Escherichia coli bacterial suspension is placed in a constant-temperature incubator at 37 ℃ and 100r/min for half an hour. Diluting the bacterial suspension with normal saline to 10 of the original concentration in a sterile table-3.5Shaking up with a vortex mixer, injecting the grafting product water solution with corresponding concentration, standing for 30s after shaking up again, placing 100 μ l on the prepared escherichia coli culture medium, wiping the applicator with alcohol, burning for 5s with an alcohol lamp, cooling to room temperature, and rapidly rotating clockwise to uniformly coat the bacterial suspension on the culture medium. The coated culture medium is placed in a constant-temperature incubator at 37 ℃, cultured for 24h, and subjected to a viable count method, blank experiments and control experiments are simultaneously carried out, each sample is parallelly measured for five times, the bacteriostasis rate is obtained, and the results are shown in the table below.
From the bacteriostatic results shown in the table above, the grafted product of maleic anhydride and disinfectant has a strong bacteriostatic effect on escherichia coli.
Example 14 production apparatus
The embodiment discloses a reaction kettle for preparing a maleic anhydride grafted polyguanidine disinfectant, which comprises a reaction kettle, a discharge mechanism, a first scraping part 300 and a second scraping part 208, wherein an exhaust pipe 104 is formed at the upper part of the reaction kettle, and the first scraping part 300 is installed on the exhaust pipe 104 and is used for scraping off crystals on the inner wall of the exhaust pipe 104; the discharging mechanism is arranged on the conveying pipe 106 at the lower end of the reaction kettle and extends into the conveying pipe 106; a second scraper member 208 is configured at the upper end of the discharge mechanism for scraping material off the bottom wall of the reactor. The working principle and the advantages of the preparation device are as follows: when crystals are attached to the inner wall of the exhaust pipe 104 to affect exhaust, an operator scrapes off the crystals on the inner wall of the exhaust pipe 104 by controlling the first scraping member 300, so that the exhaust pipe 104 is cleaned; after the cleaning is finished, an operator can detach the first scraping member 300, remove crystals on the first scraping member, and install the first scraping member on the exhaust pipe 104; the discharging mechanism is arranged in the conveying pipe 106, and drives the second scraping piece 208 to scrape the bottom wall of the reaction kettle in the process of improving the discharging of the materials in the reaction kettle, so that the materials are prevented from being deposited on the bottom wall to be condensed or separated out of crystals, the blockage of a discharging opening is avoided, and the phenomenon of crystal accumulation is avoided; in conclusion, the preparation device improves the discharging efficiency and effectively removes the crystallization on the upper inner wall of the exhaust pipe 104. As shown in fig. 11, the reaction kettle includes a kettle body 100, a discharging hopper 105 and the end cover 102, and the axes of the three coincide, wherein the kettle body 100 is of a cylindrical structure and is vertically arranged, the end cover 102 and the discharging hopper 105 are detachably connected to the upper and lower ends of the kettle body 100, respectively, and the edge of the second scraping member 208 is close to the inner wall of the discharging hopper 105. In order to facilitate the exhaust, the exhaust pipe 104 is configured on the arc-shaped surface of the end cover 102; the end cover 102 is an upwardly protruding circular arc structure, and a feed pipe 103 communicating with the inside of the reaction vessel is configured at the top of the end cover 102 (at the center of the end cover 102). The specific fixing manner of the kettle body 100 in this embodiment is as follows: a plurality of fixing lugs 101 are arranged on the outer wall of the lower part of the kettle body 100 at intervals along the circumferential direction of the kettle body, and the kettle body 100 is fixed on a bracket through the fixing lugs 101 and fixing bolts. In this embodiment, in order to prevent the mixture from being discharged out of the reaction vessel due to temperature decrease, an electric heating wire 400 spirally extending along the axis of the discharge hopper 105 is attached to the outer wall thereof. As shown in fig. 13, the first scraping member 300 includes a fixing ring 301 attached to the end of the exhaust pipe 104, and a plurality of scraping pieces 302 are formed on the fixing ring 301 at intervals in the circumferential direction thereof, the scraping pieces 302 each contacting the inner wall of the exhaust pipe 104. In order to improve the connection strength between the first scraper 300 and the exhaust pipe 104 and facilitate the removal of crystals on the first scraper 300, the scraper blades 302 are elastic blades made of metal, and the scraper blades 302 elastically expand on the inner wall of the exhaust pipe 104. In order to facilitate the operation of an operator, a mounting bar 303 extending outwards along the radial direction of the fixing ring 301 is configured on the fixing ring 301, a hand lever 304 is configured on the mounting bar 303, and the operator can hold the hand lever 304 to rotate the fixing ring 301, so that the scraping sheet 302 rotates along the axis of the exhaust pipe 104, and the crystal on the inner wall of the exhaust pipe 104 is removed. As shown in fig. 10 and 12, the discharging mechanism includes a forward and reverse rotation motor 200 and a rotation shaft 201, wherein an output shaft of the forward and reverse rotation motor 200 is coaxially connected to the rotation shaft 201, a blade 210 extending spirally along an axis of the rotation shaft 201 is configured on the rotation shaft 201, the rotation shaft 201 and the blade 210 both extend into the conveying pipe 106 from a lower end of the conveying pipe 106, a discharging port 107 is configured at a lower portion of the conveying pipe 106, when the forward and reverse rotation motor 200 is driven to rotate in a forward direction, the conveying pipe 106, the rotation shaft 201 and the blade 210 form a screw conveyor, which is beneficial to discharging a material with high viscosity through the discharging port 107, when discharging is not needed, the forward and reverse rotation motor 200 is driven to rotate in a reverse direction, and the second scraping member 208 stirs the material at the lower portion of the reaction kettle and scrapes the. In this embodiment, a cover plate 211 is detachably mounted at the lower end of the conveying pipe 106, the rotating shaft 201 extends into the conveying pipe 106 through the cover plate 211, and the rotating shaft 201 is rotatably connected with the cover plate 211. As shown in fig. 10 and 12, the rotating shaft 201 extends from the lower end of the conveying pipe 106 to the upper portion of the reaction kettle along the vertical direction, the second scraping member 208 is assembled on the rotating shaft 201 and located on the upper portion of the blade 210, and the first stirring member and the second stirring member are assembled on the rotating shaft 201 above the second scraping member 208 at intervals along the vertical direction, wherein the rotating shaft 201 is of a sectional structure, and the second stirring member, the first stirring member, the second scraping member 208 and the discharging mechanism are respectively disconnected, as shown in fig. 12, adjacent rotating shaft 201 portions are respectively connected through the first connecting sleeve 204, the second connecting sleeve 207 and the third connecting sleeve 209, so that the installation and subsequent disassembly and maintenance operations are facilitated. When the motor 200 corotation of just reversing or reverse rotation, the material is stirred and the misce bene by first stirring and second stirring, has avoided the solidification of material and the precipitation of crystallization simultaneously. As shown in fig. 12, the first stirring member includes a plurality of first mounting rods 205 uniformly arranged along the axial direction of the rotating shaft 201, each first mounting rod 205 extends outward along the radial direction of the rotating shaft 201, a plurality of first stirring rods 206 are configured on each first mounting rod 205 at intervals along the length direction thereof, and each first stirring rod 206 extends vertically upward; the second stirring piece includes evenly being provided with many second installation poles 202 along the axial of pivot 201, each second installation pole 202 radially outwards extends along pivot 201, it has many second puddlers 203 to construct along its length direction interval on each second installation pole 202, the vertical downwardly extending of each second puddler 203, and the movement track of each second puddler 203 is located between two adjacent first puddler 206 movement tracks, and like this, make the material under the stirring of first stirring piece and second stirring piece, it is more even to mix, the efficiency that the stirring was mixed has been improved.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and reference may be made to the related descriptions of other embodiments for parts that are not described or illustrated in a certain embodiment.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not substantially depart from the spirit and scope of the embodiments of the present invention, and are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a high-efficiency environment-friendly maleic anhydride grafted polyguanidine disinfectant is characterized by comprising the following steps: according to the method, an organic-inorganic mixed solvent is adopted to carry out ultrasonic-assisted dissolution on the polyhexamethylene guanidine hydrochloride before grafting, and the grafting product is subjected to rotary evaporation-sedimentation combined impurity removal and purification, so that the high-purity maleic anhydride grafted polyguanidine disinfectant is prepared efficiently; the organic-inorganic mixed solvent is a mixed solvent of absolute ethyl alcohol and water; the ultrasonic intensity of the ultrasonic-assisted dissolution is set to be 25-30W/cm3Ultrasonic frequency is 30-50KHz, and action time is 10-30 min; the row rotary evaporation-sedimentation combined impurity removal and purification operation is carried out by firstly carrying out rotary evaporation under the following process parameters: rotary steaming at 40-45 deg.C under-0.090 Mpa to-0.1005 Mpa for 15-25min, adding acetone, settling, decanting to remove supernatant, and repeating the operation for 2-4 times.
2. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the organic-inorganic mixed solvent is a mixed solvent of absolute ethyl alcohol and water; the ultrasonic intensity of the ultrasonic-assisted dissolution setting is 27.5W/cm3Ultrasonic frequency is 40KHz, and action time is 20 min; the rotary evaporation-sedimentation combined impurity removal and purification operation is carried out by firstly carrying out rotary evaporation under the following process parameters: rotary steaming at 42 deg.C under-0.095 Mpa for 20min, adding acetone, settling, decanting to remove supernatant, and repeating the operation 3 times.
3. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: in the mixed solvent of the absolute ethyl alcohol and the water, the volume ratio of the absolute ethyl alcohol to the water is (1.5-2.5): 1.
4. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: in the mixed solvent of the absolute ethyl alcohol and the water, the volume ratio of the absolute ethyl alcohol to the water is 2: 1.
5. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the steps of firstly preparing polyhexamethylene guanidine hydrochloride before grafting, taking 1, 6-hexamethylene diamine and guanidine hydrochloride as initial raw materials and polyethylene glycol as an initiator, and synthesizing the disinfectant, namely the polyhexamethylene guanidine hydrochloride by adopting a high-temperature thermal polycondensation reaction.
6. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the method firstly carries out the preparation of polyhexamethylene guanidine hydrochloride before grafting, and 1, 6-hexamethylene diamine and guanidine hydrochloride are mixed in a proportion of 1: 1, adding the mixture into a dry reaction container, introducing nitrogen by using polyethylene glycol as an initiator, heating and stirring the mixture from room temperature under the protection of nitrogen, and absorbing tail gas; heating the mixture to 60-80 ℃ from room temperature, keeping the temperature for 20min at every 10 ℃ rise within the temperature range of 60-120 ℃, keeping the temperature for 30min-60min at the temperature of 130 ℃, keeping the temperature for 20min-30min at every 10 ℃ rise when the temperature rises from 130 ℃ to 170-180 ℃, and continuing to perform constant temperature reaction for 4-7 h to complete the polymerization reaction.
7. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the method firstly carries out the preparation of polyhexamethylene guanidine hydrochloride before grafting, and 1, 6-hexamethylene diamine and guanidine hydrochloride are mixed in a proportion of 1: 1, adding the mixture into a dry reaction container, introducing nitrogen by using polyethylene glycol as an initiator, and heating and stirring from room temperature under the protection of nitrogen; and keeping the temperature for 30-60 min every time the temperature is increased by 30-50 ℃ within the temperature range of 60-160 ℃ until the temperature is increased to 170-180 ℃, and continuing to perform constant temperature reaction for 4-7 h to finish the polymerization reaction.
8. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: in the method, after polyhexamethylene guanidine hydrochloride is subjected to ultrasonic-assisted dissolution, maleic anhydride is added under the conditions of nitrogen protection and constant temperature for grafting reaction, and a crude grafting product of maleic anhydride grafted polyguanidine is obtained.
9. The preparation method of the efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: after the polyhexamethylene guanidine hydrochloride is subjected to ultrasonic-assisted dissolution, the method comprises the following steps of mixing maleic anhydride and a disinfectant according to a molar ratio of 1.2:1, adding maleic anhydride to completely dissolve the maleic anhydride to form a homogeneous system; then adding the mixture into a reaction vessel, introducing nitrogen, and reacting for 13 hours under the protection of nitrogen by heating in a water bath at 45 ℃ and magnetic stirring.
10. A reation kettle for preparing maleic anhydride grafting polyguanidine disinfectant which characterized in that: the device comprises an exhaust pipe constructed at the upper part of a reaction kettle, wherein a first material scraping part used for scraping off crystals on the inner wall of the exhaust pipe is arranged on the exhaust pipe, a material discharging mechanism extending into a conveying pipe is arranged on the conveying pipe at the lower end of the reaction kettle, and a second material scraping part used for scraping off materials on the bottom wall of the reaction kettle is constructed at the upper end of the material discharging mechanism; the reaction kettle comprises a vertically arranged cylindrical kettle body, the upper end and the lower end of the kettle body are respectively detachably connected with an end cover and a blanking hopper, and the edge of the second scraping piece is close to the inner wall of the blanking hopper; the end cover is of an upward protruding arc-shaped structure, a feeding pipe communicated with the interior of the reaction kettle is constructed at the top of the end cover, and the exhaust pipe is constructed on the end cover; a plurality of fixing lugs are arranged on the outer wall of the lower part of the kettle body at intervals along the circumferential direction of the kettle body, and the kettle body is fixed on the bracket through the fixing lugs; the outer wall of the discharging hopper is sleeved with an electric heating wire spirally extending along the axis of the discharging hopper; the first scraping piece comprises a fixing ring arranged at the end part of the exhaust pipe, a plurality of scraping pieces are formed on the fixing ring at intervals along the circumferential direction of the fixing ring, and each scraping piece is respectively contacted with the inner wall of the exhaust pipe; the scraping sheet is an elastic sheet made of a metal material, the scraping sheet is elastically expanded on the inner wall of the exhaust pipe, a mounting bar extending outwards along the radial direction of the fixing ring is constructed on the fixing ring, and a hand lever is constructed on the mounting bar; the discharging mechanism comprises a rotating shaft coaxially connected with an output shaft of a forward and reverse rotating motor, blades spirally extending along the axis of the rotating shaft are constructed on the rotating shaft, both the rotating shaft and the blades extend into the conveying pipe from the lower end of the conveying pipe, and a discharging port is constructed at the lower part of the conveying pipe; the rotating shaft extends to the upper part of the reaction kettle from the lower end of the conveying pipe along the vertical direction, the second scraping part is assembled on the rotating shaft and positioned on the upper part of the blade, and a first stirring part and a second stirring part are vertically and upwardly assembled on the rotating shaft above the second scraping part at intervals; the first stirring piece comprises a plurality of first mounting rods which are uniformly arranged along the axial direction of the rotating shaft, each first mounting rod extends outwards along the radial direction of the rotating shaft, a plurality of first stirring rods are constructed on each first mounting rod at intervals along the length direction of the first mounting rod, and each first stirring rod extends upwards in the vertical direction; the second stirring piece comprises a plurality of second mounting rods which are evenly arranged along the axial direction of the rotating shaft, each second mounting rod extends outwards along the radial direction of the rotating shaft, a plurality of second stirring rods are constructed on each second mounting rod along the length direction of the second mounting rod at intervals, each second stirring rod extends downwards vertically, and the motion trail of each second stirring rod is located between the motion trails of two adjacent first stirring rods.
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