CN108641087B - Diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment and preparation method and application thereof - Google Patents
Diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a diblock macromolecular quaternary ammonium salt containing a polysiloxane chain segment, and a preparation method and application thereof. The preparation method comprises the following steps: firstly, synthesizing polysiloxane with vinyl at a single end; through click reaction with mercaptoethanol, polysiloxane with hydroxyl at one end is synthesized; then polysiloxane with single hydroxyl reacts with 2-bromine isobutyryl bromide to synthesize polysiloxane macroinitiator, and then DMAPMA is initiated to carry out ATRP polymerization; and finally, carrying out quaternization by using benzyl chloride to synthesize the diblock macromolecular quaternary ammonium salt containing the polysiloxane chain segment. The amphiphilic macromolecular quaternary ammonium salt has good adsorption and permeation capability on sclerotium of rhizoctonia solani, so that the amphiphilic macromolecular quaternary ammonium salt has a good inhibition effect on the germination of sclerotium.
Description
Technical Field
The invention belongs to the field of synthesis and application of high polymer materials, and particularly relates to a diblock macromolecular quaternary ammonium salt containing a polysiloxane chain segment, and a preparation method and application thereof.
Background
Rhizoctonia solani, also known as leaf streak disease, is commonly known as flower foot stalk, is widely distributed in the world major rice producing countries and has become the first three diseases of rice in China. Rhizoctonia solani is a soil-borne disease caused by rhizoctonia solani (r.solani), mainly by vegetative propagation. The bacterium exists mainly in two forms, namely hypha and sclerotium, under the natural state. One important reason for serious damage of rice sheath blight is the infection cycle of sclerotium germination to form hyphae, hyphae infection of host and hyphae aggregation under forced condition to form sclerotium.
At present, the prevention and control of the rice sheath blight disease are mainly performed by killing hyphae of the rice sheath blight fungus, such as the use of validamycin, but no good method is available for killing sclerotia. This is because the sclerotium of Rhizoctonia solani consists of two layers of structure, the inner layer is living cells, and the outer layer is a large number of empty cells (reference 1: Teruyoshi Hashiba, Shizuo Mogi, Developmental changes in sclerita of rice sheath bright funus, Phytopathology,1975,65: 159; reference 2: Pensha fur, Zhang Rui, Zhang Shiguang, Zhang Shi. And the small-molecule pesticide is difficult to gather on the surface of the sclerotium due to the insufficient adsorption performance and then permeate into the interior of the sclerotium. This results in the need to regularly spray a large amount of pesticide to the rice field every year to prevent the harm caused by the germination of sclerotium. In addition, small-molecule pesticides are easy to lose with irrigation water due to insufficient adsorbability, so that a large amount of spraying is needed to make up for the deficiency of the efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a diblock macromolecular quaternary ammonium salt containing a polysiloxane chain segment.
Another object of the present invention is to provide a diblock macromolecular quaternary ammonium salt containing a polysiloxane segment obtained by the above preparation method.
The invention also aims to provide application of the diblock macromolecular quaternary ammonium salt containing the polysiloxane chain segment.
The purpose of the invention is realized by the following technical scheme: a preparation method of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments comprises the following steps:
(1) synthesis of a vinyl-terminated polydimethylsiloxane (PDMS-Vi): adding hexamethylcyclotrisiloxane (D) into organic solvent A3) In the atmosphere of inert gas, initiating a polymerization reaction by using n-butyllithium, and finally adding dimethylvinylchlorosilane to terminate the polymerization reaction; purifying the product obtained by the reaction to obtain a transparent oily liquid product, namely the polydimethylsiloxane with single terminal vinyl;
(2) synthesis of a Single-terminal hydroxyl polydimethylsiloxane (PDMS-OH): mixing an organic solvent B, PDMS-Vi, mercaptoethanol and a catalyst to obtain a clear solution, initiating a free radical addition reaction by using ultraviolet light, and purifying a product obtained by the reaction to obtain the polydimethylsiloxane with single end hydroxyl;
(3) synthesis of polydimethylsiloxane (PDMS-Br) with bromine at one end: adding PDMS-OH and triethylamine into the organic solvent C, adding a mixed solution formed by 2-bromoisobutyryl bromide and the organic solvent C, and mixing and reacting in an inert gas atmosphere; purifying a product obtained by the reaction to obtain polydimethylsiloxane with bromine at the end;
(4) synthesis of a diblock copolymer of polysiloxane and of polydimethylaminoethyl methacrylate (PDMS-b-PDMAEMA): mixing an organic solvent D, PDMS-Br, dimethylaminoethyl methacrylate (DMAEMA), CuBr and N, N, N' -pentamethyl divinyl triamine (PMDETA), carrying out polymerization reaction in an inert gas atmosphere, and purifying a product obtained by the reaction to obtain a light yellow viscous liquid product, namely a diblock copolymer of polysiloxane and dimethylaminoethyl methacrylate;
(5) synthesis of diblock macromolecular Quaternary ammonium salt containing polysiloxane segment (PDMS-b-QPDMAEMA): PDMS-b-PDMAEMA and benzyl chloride are dissolved in an organic solvent E to react in an inert gas atmosphere, and a product is purified to obtain the diblock macromolecular quaternary ammonium salt containing the polysiloxane chain segment.
The organic solvent A, B, C, D, E described above is used to dissolve the reaction mass and does not participate in the reaction itself.
The inert gas described hereinbefore is preferably nitrogen.
The organic solvent A in the step (1) is preferably tetrahydrofuran.
The volume usage amount of the solution organic solvent A in the step (1) is preferably 1.5-4 times (mL: g) of the mass of the hexamethylcyclotrisiloxane monomer; more preferably 1.8 to 2 times.
The n-butyllithium, hexamethylcyclotrisiloxane and dimethylvinylchlorosilane in the step (1) are mixed according to a molar ratio of 1: (13.5 to 134.9): (1-1.2).
The polymerization reaction in the step (1) is preferably carried out for 12-36 h at 0-5 ℃.
The purification step described in step (1) is preferably: and removing the solvent and the unpolymerized small molecule raw material by reduced pressure distillation, and then filtering to remove by-product lithium chloride powder to obtain the purified PDMS-Vi.
The organic solvent B in the step (2) is preferably tetrahydrofuran.
The mass usage amount of the organic solvent B in the step (2) is preferably 1-4 times of the mass of PDMS-Vi; more preferably 2 to 3 times.
The catalyst in the step (2) is benzoin dimethyl ether.
And (3) proportioning the PDMS-Vi and the mercaptoethanol in the step (2) according to the molar ratio of 1: 1.
The amount of the catalyst used in the step (2) is preferably as follows: the mass ratio of the catalyst is 1: 0.02.
The condition of the free radical addition reaction in the step (2) is preferably reaction at room temperature for 30-90 min; preferably 30-60 min.
The room temperature is 10-35 ℃; more preferably 20 to 25 ℃.
The preferable wavelength of the ultraviolet light in the step (2) is 350-365 nm; more preferably, the wavelength is 365 nm.
The purification steps described in step (2) are preferably as follows: removing the solvent by reduced pressure distillation, extracting the obtained viscous liquid with methanol, removing unreacted raw materials, repeating for more than 0 times, and then distilling under reduced pressure to obtain the purified PDMS-OH.
The repetition frequency is preferably 2-3 times.
The organic solvent C in the step (3) is tetrahydrofuran.
The mass usage amount of the organic solvent C in the step (3) is preferably 1.3-3 times of the mass of PDMS-OH; more preferably 2 to 2.5 times.
And (3) the PDMS-OH, triethylamine and 2-bromoisobutyryl bromide in the step (3) are added according to a molar ratio of 1: (1-1.2): (1-1.2).
The reaction conditions in the step (3) are preferably 1 hour at 0 ℃ and then 24 hours at room temperature.
The room temperature is 10-30 ℃; more preferably 20 to 25 ℃.
The purification steps described in step (3) are preferably as follows: filtering to remove byproduct ammonium salt powder, distilling under reduced pressure to remove solvent, extracting with methanol to remove unreacted raw materials, repeating for more than 0 times, and distilling under reduced pressure to obtain purified PDMS-Br.
The repetition frequency is preferably 2-3 times.
The organic solvent D in the step (4) is preferably isopropanol.
The dosage of the organic solvent D in the step (4) is preferably 3-8 times of the mass of dimethylaminoethyl methacrylate; more preferably 4 to 6 times.
And (3) the PDMS-Br, the dimethylaminoethyl methacrylate, the CuBr and the N, N, N' -pentamethyl divinyl triamine in the step (4) are added according to a molar ratio of 1: 18: (1-1.2): (1-1.2).
The reaction condition in the step (4) is preferably reaction for 5-20 h at 40-80 ℃; more preferably, the reaction is carried out for 6 to 10 hours at the temperature of 45 to 55 ℃; most preferably at 50 ℃ for 8 h.
The purification step described in step (4) is preferably as follows: adding neutral alumina, stirring until the solution turns from green to colorless, then filtering out powder, and finally rotatably evaporating the solvent and unreacted monomers to obtain the purified PDMS-b-PDMAEMA.
The organic solvent E in the step (5) is preferably a mixed solution of toluene and ethanol in a mass ratio of 1: 1.
The volume usage amount of the organic solvent E in the step (5) is preferably 2-3 times of the mass of the PDMS-b-PDMAEMA.
And (3) proportioning the PDMS-b-PDMAEMA and the benzyl chloride in the step (5) according to a molar ratio of 1: 18.
The reaction condition in the step (5) is preferably reaction at 60-80 ℃ for 16-32 h; more preferably, the reaction is carried out for 20-28 h at 65-75 ℃; most preferably at 70 ℃ for 24 h.
The purification in the step (5) preferably comprises the following steps: and (3) distilling a part of solvent under reduced pressure, adding a large amount of anhydrous ether to precipitate quaternary ammonium salt, pouring out supernatant, and drying in a vacuum oven at 50 ℃ to obtain the diblock macromolecular quaternary ammonium salt PDMS-b-QPDMAEMA containing the polysiloxane chain segment.
PDMS with different molecular weights can be prepared by controlling the feeding ratio of the D3 monomer to n-butyllithium and the polymerization reaction time in the step (1), and PDMS-b-PDMAEMA with different lengths of the chain segments of the dimethylaminoethyl methacrylate can be obtained by controlling the feeding ratio of the DMAEMA monomer to the PDMS-Br in the step (5).
A diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments is obtained by the preparation method.
The polysiloxane-segment-containing diblock macromolecular quaternary ammonium salt is preferably polysiloxane-segment-containing diblock macromolecular quaternary ammonium salt with the following characteristics: the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: and (13-135) QPDMAEMA, wherein the length of the PDMS block is 1-10 kDa, and the length of the QPDMAEMA block is 5 kDa.
The application of the diblock macromolecular quaternary ammonium salt containing the polysiloxane chain segment in preventing and treating rice sheath blight disease is particularly used for inhibiting the germination of sclerotium.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides a preparation method of amphiphilic diblock macromolecular quaternary ammonium salt (PDMS-b-QPDMAEMA) containing polysiloxane segments. Compared with the prior art, the method has the advantages that after the ring opening of the D3 anion is carried out in the first step, the dimethylvinylchlorosilane is used for carrying out end capping to prepare the silicone oil with the single-terminal vinyl group, and the molecular weight of the silicone oil with the single-terminal vinyl group can be accurately controlled by controlling the molar ratio of the initiator to the D3. And secondly, by utilizing click reaction, hydroxyl is grafted into a macromolecular chain to obtain hydroxyl-terminated silicone oil, so that the method is efficient and convenient, no by-product is generated, the subsequent purification work is optimized, and the yield is greatly improved. Finally, the ATRP is utilized to graft DMAPMA on PDMS to form a two-block copolymer, and the molecular weight of the PDMAEMA chain segment is accurately controlled. By accurately regulating and controlling the molecular weight of the two blocks, the amphiphilic macromolecular quaternary ammonium salt with good sclerotium killing capability is finally obtained.
Drawings
FIG. 1 is a chemical reaction scheme of examples 1 to 6.
FIG. 2 is an infrared characterization and nuclear magnetic spectrum of PDMS-Vi, PDMS-OH, PDMS-Br, PDMS-b-PDMAEMA and PDMS-b-QPDMAEMA of example 1.
FIG. 3 is a schematic diagram showing changes in surface contact angle before and after the sclerotium rolfsii was immersed in a 1g/L aqueous solution prepared from PDMS-b-QPDMAEMA synthesized in examples 1 to 6 for 1 hour.
FIG. 4 is a schematic diagram showing the Minimum Inhibitory Concentration (MIC) and minimum bactericidal concentration (MFC) of the mycelia of P.solani synthesized in examples 1 to 6.
FIG. 5 is a schematic diagram showing the germination inhibition effect of PDMS-b-QPDMAEMA synthesized in examples 1 to 6 on sclerotinia sclerotiorum sclerotium; wherein 5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC in X coordinate refer to 5, 10, 15 and 20 times of the corresponding Minimum Inhibitory Concentration (MIC) of the sterile aqueous solution prepared from PDMS-b-QPDMAEMA, respectively; 7D, 14D, 21D, 28D and 35D in the Y coordinate indicate that the sclerotium is soaked in a sterile aqueous solution prepared from PDMS-b-QPDMAEMA for 7 days, 14 days, 21 days, 28 days and 35 days respectively; the inhibition rate of sclerotium germination in the Z coordinate refers to the percentage of the number of sclerotium inactivated after 40 sclerotium are soaked in a sterile aqueous solution prepared from PDMS-b-QPDMAEMA.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The reagents used in the present invention are all commercially available.
Example 1
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA ═ 27:18, PDMS block length 2kDa, QPDMAEMA block length 5 kDa. The preparation process is shown in figure 1, and comprises the following specific steps:
(1) in a schlenk bottle equipped with a magnetic stirrer, 50g D was added3And then sealing the bottle by a silica gel plug, vacuumizing the bottle, introducing high-purity nitrogen, and repeating the operation for three times to ensure that the bottle is full of nitrogen. Injecting 100mL of dry tetrahydrofuran by a syringe to dissolve D3After a clear solution was obtained, 10mL of an n-hexane solution containing 2.5mol/L of n-butyllithium was injected at 0 ℃ to initiate ring-opening polymerization of anions. Stirring at 0 deg.C for about 12 hr, collecting3.02g of dimethylvinylchlorosilane are poured into a Schlenk flask and stirring is continued for about 1h to complete termination of the polymerization. And (3) carrying out rotary evaporation on the reaction liquid at 120 ℃ to remove the solvent and the small molecular monomer, precipitating a large amount of by-product lithium chloride powder, and filtering to obtain a colorless and transparent viscous liquid product PDMS-Vi, wherein an infrared spectrogram and a nuclear magnetic spectrogram of the viscous liquid product PDMS-Vi are respectively shown in FIGS. 2(A) and (B).
(2) 40g of PDMS-Vi, 1.57g of mercaptoethanol and 0.8g of benzoin dimethyl ether are added into a transparent quartz flask provided with a magnetic stirrer; 80.0g of tetrahydrofuran was added to the above starting material to form a colorless transparent solution. The reaction is kept stirring for 60min under the irradiation of ultraviolet light with the wavelength of 365 nm. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a viscous liquid crude product, which was mixed with methanol, charged in a separatory funnel and sufficiently shaken, and the mixture was stood still to take off the liquid in the lower layer and repeated three times. And finally, carrying out reduced pressure distillation to remove residual methanol to obtain a colorless viscous liquid product PDMS-OH, wherein an infrared spectrogram and a nuclear magnetic spectrogram of the product are respectively shown in FIGS. 2(A) and (B).
(3) 30g of PDMS-OH and 1.52g of triethylamine are added into a glass flask provided with a magnetic stirring bar, 40g of tetrahydrofuran is used for dissolving, 3.45g of 2-bromoisobutyryl bromide is dissolved in 20g of tetrahydrofuran and placed in a titration funnel, and the solution is dripped into the flask at the speed of 1 drop/5 s for reaction at the temperature of 0 ℃ for 1h, and then the reaction is carried out at the normal temperature for 24 h. After the reaction is finished, filtering and distilling under reduced pressure to remove tetrahydrofuran, mixing the crude product with methanol, placing the mixture in a separating funnel, fully shaking the mixture, standing the mixture to remove the liquid of the lower layer, repeating the operation for three times, and finally distilling under reduced pressure to remove residual methanol to obtain a final product PDMS-Br, wherein infrared spectrograms and nuclear magnetic spectrograms of the final product PDMS-Br are respectively shown in figures 2(A) and (B).
(4) Adding 0.62g of CuBr into a schlenk bottle with a magnetic stirrer, adding 50mL of glacial acetic acid, stirring for 15min, pouring out liquid, keeping powder, and repeating the steps for three times; then adding 50mL of absolute ethyl alcohol, stirring for 10min, pouring out liquid, keeping powder, and repeating the steps for three times; and finally adding 7.22g of PDMS-Br, 10g of DMAEMA, 0.68g of PMDETA and 45g of isopropanol into the flask, sealing the flask by using a silica gel plug, vacuumizing the flask, introducing high-purity nitrogen, repeating the operation for three times to ensure that the flask is filled with the nitrogen, and reacting for 8 hours at the temperature of 50 ℃. After the reaction was completed, isopropanol was distilled off under reduced pressure, and 100mL of acetone was added to dissolve the isopropanol. Then adding a large amount of neutral alumina until the solution turns from green to colorless, filtering out solid powder, and distilling the collected liquid under reduced pressure to remove acetone to obtain the final product PDMS-B-PDMAEMA, wherein the infrared spectrogram and the nuclear magnetic spectrogram are respectively shown in fig. 2(A) and (B).
(5) 10g of PDMS-b-PDMAEMA and 20mL of a mixed solution (obtained by mixing toluene and ethanol according to a volume ratio of 1: 1) are added into a three-neck glass flask with a magnetic stirrer, 4.68g of benzyl chloride is added, nitrogen is introduced, and the mixture is subjected to condensation reflux reaction at 70 ℃ for 24 hours. After the reaction is finished, a part of methanol is distilled under reduced pressure, then a large amount of ether is added to separate out a solid, most of supernatant is poured out after the mixture is kept stand for a period of time, and the supernatant is put into a vacuum oven to be dried, so that the quaternary ammonium salt PDMS-b-QPDMAEMA, which is abbreviated as S for short, is obtained2Q5。
Example 2
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA ═ 40:18, PDMS block length 3kDa, QPDMAEMA block length 5 kDa. The preparation process is shown in fig. 1, and is substantially the same as the step of example 1, except that:
in the step (1), the injection amount of n-butyllithium is 6.67mL, the stirring time at 0 ℃ is about 18h, and the feeding amount of dimethylvinylchlorosilane is 2.01 g;
the feeding amount of the mercaptoethanol in the step (2) is 1.04 g;
in the step (3), the feeding amount of triethylamine and 2-bromine isobutyryl bromide is 1.01g and 2.30g respectively;
the feeding amount of PDMS-Br in the step (4) is 10.83 g;
the dosage of the benzyl chloride in the step (5) is 3.87 g.
The obtained product is abbreviated as S3Q5。
Example 3
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA ═ 54:18, PDMS block length 4kDa, QPDMAEMA block length 5 kDa. The preparation process is shown in fig. 1, and is substantially the same as the step of example 1, except that:
in the step (1), the injection amount of n-butyllithium is 5.00mL, the stirring time at 0 ℃ is about 24 hours, and the feeding amount of dimethylvinylchlorosilane is 1.51 g;
the feeding amount of the mercaptoethanol in the step (2) is 0.78 g;
in the step (3), the feeding amount of triethylamine and the feeding amount of 2-bromine isobutyryl bromide are respectively 0.76g and 1.73 g;
the feeding amount of PDMS-Br in the step (4) is 14.44 g;
the feeding amount of the benzyl chloride in the step (5) is 3.30 g;
the obtained product is abbreviated as S4Q5。
Example 4
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA 67:18, PDMS 5kDa long and QPDMAEMA 5kDa long. The preparation process is shown in fig. 1, and is substantially the same as the step of example 1, except that:
in the step (1), the injection amount of n-butyllithium is 4.00mL, the stirring time at 0 ℃ is about 30h, and the feeding amount of dimethylvinylchlorosilane is 1.21 g;
the feeding amount of the mercaptoethanol in the step (2) is 0.63 g;
in the step (3), the feeding amount of triethylamine and the feeding amount of 2-bromine isobutyryl bromide are respectively 0.61g and 1.38 g;
the feeding amount of PDMS-Br in the step (4) is 18.05 g;
the feeding amount of the benzyl chloride in the step (5) is 2.87 g;
the obtained product is abbreviated as S5Q5。
Example 5
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA ═ 108:18, PDMS block length 8kDa, QPDMAEMA block length 5 kDa. The preparation process is shown in fig. 1, and is substantially the same as the step of example 1, except that:
in the step (1), the injection amount of n-butyllithium is 2.50mL, the stirring time at 0 ℃ is about 36h, and the feeding amount of dimethylvinylchlorosilane is 0.76 g;
the feeding amount of the mercaptoethanol in the step (2) is 0.39 g;
in the step (3), the feeding amount of triethylamine and the feeding amount of 2-bromine isobutyryl bromide are respectively 0.38g and 0.87 g;
the feeding amount of PDMS-Br in the step (4) is 28.88 g;
the feeding amount of the benzyl chloride in the step (5) is 2.07 g;
the obtained product is abbreviated as S8Q5。
Example 6
Preparation of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment:
the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA ═ 135:18, PDMS block length 10kDa, QPDMAEMA block length 5 kDa. The preparation process is shown in fig. 1, and is substantially the same as the procedure of example 1, except that:
in the step (1), the injection amount of n-butyllithium is 2.00mL, the stirring time at 0 ℃ is about 36h, and the feeding amount of dimethylvinylchlorosilane is 0.61 g;
the feeding amount of the mercaptoethanol in the step (2) is 0.32 g;
in the step (3), the feeding amount of triethylamine and the feeding amount of 2-bromine isobutyryl bromide are respectively 0.31g and 0.69 g;
the feeding amount of PDMS-Br in the step (4) is 36.10 g;
the feeding amount of the benzyl chloride in the step (5) is 1.75 g;
the obtained product is abbreviated as S10Q5。
Effects of the embodiment
Rhizoctonia solani (R.solani AG-1-IA) No. 119 strain is provided for the fungi research laboratory of the Phytopathology department of resource environmental institute of southern China agricultural university, is separated from sheath of rice disease which shows obvious symptom of rhizoctonia solani, is highly pathogenic, and is the dominant strain of Guangzhou province (published in the literature, "Weekly, Yanmei, Lilin, etc.. the influence of culture medium on the growth of hyphae and sclerotia of Rhizoctonia solani. the university of southern China school, 2002,23(3): 33-35."). Culturing and maturing the sclerotium in an incubator at 28 ℃ and a PDA culture medium for 7-14 days in a laboratory to obtain mature sclerotium.
Firstly, the following performance tests were performed on the above examples 1 to 6:
(1) method for testing adsorption capacity of sclerotium of rhizoctonia solani
Firstly, ultrapure water is used as a solution, an optical contact angle measurement analyzer (DropMeter A-100) is used for testing the contact angle of the surface of sclerotium, then a quaternary ammonium salt aqueous solution (the quaternary ammonium salt polymer prepared in the examples 1-6) with the concentration of 1g/L is prepared, the sclerotium is soaked in the quaternary ammonium salt aqueous solution for 1h, the sclerotium is taken out and slightly rinsed by the ultrapure water, the contact angle of the surface of the sclerotium is tested again after the sclerotium is naturally dried, and the adsorption quantity of the diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments to the sclerotium is judged according to the reduction degree of the contact angle.
(2) Test for bacteriostatic effect of rhizoctonia solani hyphae
Selecting appropriate amount of mycelium from potato glucose medium (PD medium), grinding with 1mL homogenizer, diluting with PD, and counting with blood counting plate to control the concentration of bacterial suspension at 105～106CFU/mL range. Taking a proper amount of quaternary ammonium salt polymer, adding PD liquid culture medium, and diluting the polymer into a series of concentrations with gradient. And sequentially adding the prepared polymer mixed solution into a cell culture plate (96 holes) according to the sequence from high concentration to low concentration, adding 100 mu L of polymer solution into each hole, adding 100 mu L of bacterial suspension, and uniformly mixing by blowing. Two groups of controls are set, namely adding PD with the same volume or diluting bacterial suspension by one time respectively; each treatment was repeated at least 3 times. Culturing at 28 deg.C for 2 d. After 2 days of cell culture plate culture, 50. mu.L of 5% TTC dye was added to each well, mixed well and incubated at 28 ℃ to incubateThe chemical incubator was incubated for 2h in the absence of light, and the lowest polymer concentration of the non-growing bacteria (i.e., not red) was taken as the MIC. After the MIC test was completed, 100. mu.L of each of the samples was inoculated onto a blank potato glucose solid medium plate (PDA plate) at about 4 to 5 concentrations from the MIC to the polymer high concentration, and gently pushed away by an applicator, and cultured in a constant temperature incubator at 28 ℃ for 2 days, and the growth of a sterile body was observed, and the polymer concentration at which the number of colonies in plate culture was less than 5 was used as MFC.
(3) Test for germination inhibition effect of rhizoctonia solani sclerotium
Weighing a proper amount of quaternary ammonium salt PDMS-b-QPDMAEMA, sterilizing the quaternary ammonium salt PDMS-b-QPDMAEMA for 20min under an ultraviolet lamp, diluting the quaternary ammonium salt PDMS-b-QPDMAEMA into 5 XMIC, 10 XMIC, 15 XMIC and 20 XMIC respectively with sterile water, and fixing the volume to 40mL, wherein the control is sterile water with the same volume. The dried sclerotia were soaked in the above quaternary ammonium salt solutions of different concentrations, each treatment soaking 200 sclerotia, and incubated at 8 ℃ for 35 d. Every 7 days, 40 sclerotia were randomly picked for sclerotium germination experiments per treatment. PDA plates were prepared with quaternary ammonium concentrations of 5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC, respectively, and the sclerotia were transferred to the plates with 10 sclerotia per plate, four replicates per treatment. After culturing at 28 ℃ for 1d, photographing and counting the germination inhibition rate, and picking ungerminated sclerotia for carrying out a section germination experiment. The nuclei were cut into four pieces with sterilized razor blades and transferred to plates having concentrations of 5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC, cultured for 2d at 28 ℃, and the number of 4 non-germinated nuclei was counted.
(4) Toxicity testing on silkworms and Kunming mice.
Refer to GB/T31270.11-2014 chemical pesticide environmental safety evaluation test guidelines-part 11: the acute toxicity test of silkworm adopts the leaf soaking method, and the specific operation is as follows: silkworms of 2 years old were selected, 5 concentrations were set for each drug, and a blank control was set, and 3 replicates for the control group and each concentration were set. Each group of 20 silkworms is placed in a culture medium of 90 mm. Preparing medicinal liquids with different concentrations by adopting a weighing method, immersing 1.0g of vein-removed mulberry leaves in 10mL of the medicinal liquid for 10s (the mulberry leaves in a control group are treated by deionized water), feeding the silkworm twice a day after drying, and placing a piece of water-absorbing cotton with proper size at the edge of a culture dish to keep humidity. The number of deaths and toxic symptoms of the tested silkworms at 24h, 48h, 72h and 96h were observed and recorded. Using SPSS processing data, the virulence regression equation and median lethal concentration (LC50) of three different quaternary ammonium salts on silkworms were determined.
According to GB 15193.3-2014 national food safety standard acute oral toxicity test, an oral gavage method is adopted, and before the test, test mice are fasted for 4-6 hours and freely drink water. The specific operation method comprises the following steps: dividing the mice into 6 groups, weighing 10 mice in each group, determining the gavage amount of the quaternary ammonium salts with three different structures according to the weight of the mice, and gavage PBS with the same volume through the mouth of a control group. After gavage, the mice were fasted for 1 to 2 hours, fed after observation of no obvious problems, and observed for the state, weight and diet of the mice within 48 hours and 14 days, and the death of the mice in each treatment group was counted. The data were processed using AOT425 software to determine the median lethality (LD50) and confidence intervals for mice for three different classes of quats.
Second, the detection result
The results are shown in FIGS. 3 to 5 and Table 1.
In FIG. 3, the contact angles of the surface of the sclerotium were decreased to different degrees after soaking the aqueous solution of the quaternary ammonium salt PDMS-b-QPDMAEMA, which shows that the quaternary ammonium salt PDMS-b-QPDMAEMA was stably adsorbed on the surface of the sclerotium, and that the adsorption amount of the quaternary ammonium salt PDMS-b-QPDMAEMA (quaternary ammonium salt polymers prepared in examples 3 and 4) to the sclerotium was the maximum when the molecular weight of the polysiloxane segment was 4000 and 5000. FIG. 4 shows that the Minimum Inhibitory Concentration (MIC) and the minimum bactericidal concentration (MFC) of the quaternary ammonium salt PDMS-b-QPDMAEMA to rhizoctonia solani hyphae are both 40 mug/mL basically, and the bacteriostatic effect is good.
FIG. 5 shows that the quaternary ammonium salt PDMS-b-QPDMAEMA has the effect of inhibiting germination of Rhizoctonia solani and the effect is optimized when the siloxane segment has a molecular weight of 5000 (quaternary ammonium salt polymer prepared in example 4).
In Table 1, the half lethal concentrations (LC50) of the quaternary ammonium salt PDMS-b-QPDMAEMA to the silkworms are all larger than 2000mg/L, which shows that the quaternary ammonium salt PDMS-b-QPDMAEMA is nontoxic to the silkworms; the half-lethal dose (LD50) of PDMS-b-QPDMAEMA to Kunming mice is more than 2000mg/L, and the PDMS-b-QPDMAEMA is near to actual non-toxicity.
TABLE 1
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments is characterized by comprising the following steps:
(1) synthesis of a polydimethylsiloxane having a single terminal vinyl group: adding hexamethylcyclotrisiloxane into an organic solvent A, initiating a polymerization reaction by using n-butyllithium in an inert gas atmosphere, and finally adding dimethylvinylchlorosilane to terminate the polymerization reaction; purifying the product obtained by the reaction to obtain a transparent oily liquid product, namely the polydimethylsiloxane with single terminal vinyl;
(2) synthesis of a polydimethylsiloxane having a single hydroxyl group: mixing an organic solvent B, polydimethylsiloxane with single terminal vinyl, mercaptoethanol and a catalyst to obtain a clear solution, initiating a free radical addition reaction by using ultraviolet light, and purifying a product obtained by the reaction to obtain polydimethylsiloxane with single terminal hydroxyl;
(3) and (3) synthesizing polydimethylsiloxane with bromine at one end: adding polydimethylsiloxane with single-end hydroxyl and triethylamine into an organic solvent C, adding a mixed solution formed by 2-bromoisobutyryl bromide and the organic solvent C, and carrying out mixed reaction in an inert gas atmosphere; purifying a product obtained by the reaction to obtain polydimethylsiloxane with bromine at the end;
(4) synthesis of a diblock copolymer of polysiloxane and of Polymethylaminoethyl methacrylate: mixing an organic solvent D, polydimethylsiloxane with bromine at the end group, dimethylaminoethyl methacrylate, CuBr and N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine, carrying out polymerization reaction in an inert gas atmosphere, and purifying a product obtained by the reaction to obtain a light yellow viscous liquid product which is a two-block copolymer of polysiloxane and dimethylaminoethyl methacrylate;
(5) synthesis of diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment: dissolving a diblock copolymer of polysiloxane and poly (dimethylaminoethyl methacrylate) and benzyl chloride in an organic solvent E, reacting in an inert gas atmosphere, and purifying a product to obtain a diblock macromolecular quaternary ammonium salt containing a polysiloxane chain segment;
the organic solvent A in the step (1) is tetrahydrofuran;
the organic solvent B in the step (2) is tetrahydrofuran;
the organic solvent C in the step (3) is tetrahydrofuran;
the organic solvent D in the step (4) is isopropanol;
the organic solvent E in the step (5) is a mixed solution of toluene and ethanol in a mass ratio of 1: 1.
2. The method for preparing the diblock macromolecular quaternary ammonium salt containing a polysiloxane segment according to claim 1, characterized in that:
the n-butyllithium, hexamethylcyclotrisiloxane and dimethylvinylchlorosilane in the step (1) are mixed according to a molar ratio of 1: (13.5 to 134.9): (1-1.2) proportioning;
the polydimethylsiloxane with single terminal vinyl in the step (2) and the mercaptoethanol are mixed according to the molar ratio of 1: 1;
and (3) the single-end hydroxyl polydimethylsiloxane, the triethylamine and the 2-bromine isobutyryl bromide in the step (3) are mixed according to a molar ratio of 1: (1-1.2): (1-1.2) proportioning;
the polydimethylsiloxane with bromine at the end, dimethylaminoethyl methacrylate, CuBr and N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine in the step (4) are added according to the molar ratio of 1: 18: (1-1.2): (1-1.2) proportioning;
the two-block copolymer of polysiloxane and poly (dimethylaminoethyl methacrylate) in the step (5) and the benzyl chloride are mixed according to the molar ratio of 1: 18.
3. The method for preparing the diblock macromolecular quaternary ammonium salt containing a polysiloxane segment according to claim 1, characterized in that:
the catalyst in the step (2) is benzoin dimethyl ether.
4. The method for preparing the diblock macromolecular quaternary ammonium salt containing a polysiloxane segment according to claim 1, characterized in that:
the volume consumption of the solution organic solvent A in the step (1) is 1.5-4 times of the mass of the hexamethylcyclotrisiloxane monomer;
the mass amount of the organic solvent B in the step (2) is 1-4 times of that of the single-end vinyl polydimethylsiloxane;
the dosage of the catalyst in the step (2) is as follows according to the weight ratio of the polydimethylsiloxane with single terminal vinyl: catalyst = mass ratio 1: 0.02;
the mass amount of the organic solvent C in the step (3) is 1.3-3 times of that of the single-end hydroxyl polydimethylsiloxane;
the mass amount of the organic solvent D in the step (4) is 3-8 times of that of dimethylaminoethyl methacrylate;
the volume consumption of the organic solvent E in the step (5) is 2-3 times of the mass of the two-block copolymer of polysiloxane and poly (dimethylaminoethyl methacrylate).
5. The method for preparing the diblock macromolecular quaternary ammonium salt containing a polysiloxane segment according to claim 1, characterized in that:
the polymerization reaction in the step (1) is carried out for 12-36 h at 0-5 ℃;
the condition of the free radical addition reaction in the step (2) is reaction at room temperature for 30-90 min;
the ultraviolet light in the step (2) is ultraviolet light with the wavelength of 350-365 nm;
the reaction condition in the step (3) is that the reaction is carried out for 1h at 0 ℃, and then the reaction is carried out for 24h at room temperature;
the reaction condition in the step (4) is that the reaction is carried out for 5-20 h at the temperature of 40-80 ℃;
the reaction condition in the step (5) is that the reaction is carried out for 16-32 hours at the temperature of 60-80 ℃.
6. The method for preparing the diblock macromolecular quaternary ammonium salt containing a polysiloxane segment according to claim 1, characterized in that:
the purification step in the step (1) is as follows: removing the solvent and the unpolymerized micromolecule raw materials by reduced pressure distillation, and then filtering to remove by-product lithium chloride powder to obtain purified single-terminal vinyl polydimethylsiloxane;
the purification steps described in step (2) are as follows: removing the solvent by reduced pressure distillation, extracting the obtained viscous liquid with methanol, removing unreacted raw materials, repeating for more than 0 times, and then obtaining purified single-end hydroxyl polydimethylsiloxane by reduced pressure distillation;
the purification steps described in step (3) are as follows: filtering to remove byproduct ammonium salt powder, distilling under reduced pressure to remove solvent, extracting with methanol to remove unreacted raw materials, repeating for more than 0 times, and distilling under reduced pressure to obtain purified polydimethylsiloxane with bromine at one end;
the purification steps described in step (4) are as follows: adding neutral alumina, stirring until the solution turns from green to colorless, then filtering out powder, and finally, rotatably evaporating out the solvent and unreacted monomers to obtain a purified two-block copolymer of polysiloxane and dimethylaminoethyl methacrylate;
the purification step in the step (5) is as follows: and (3) distilling a part of solvent under reduced pressure, adding a large amount of anhydrous ether to precipitate quaternary ammonium salt, pouring out supernatant, and drying in a vacuum oven at 50 ℃ to obtain the diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments.
7. A diblock macromolecular quaternary ammonium salt containing polysiloxane chain segments is characterized in that: the preparation method of any one of claims 1 to 6.
8. The polysiloxane segment-containing diblock macromolecular quaternary ammonium salt according to claim 7, characterized in that: the diblock macromolecular quaternary ammonium salt containing the polysiloxane chain segment is characterized by comprising the polysiloxane chain segment: the polymerization degree ratio of the polysiloxane block chain segment to the quaternized dimethylaminoethyl methacrylate chain segment is PDMS: QPDMAEMA = (13-135), 18, the length of the PDMS block is 1-10 kDa, and the length of the QPDMAEMA block is 5 kDa.
9. Use of the polysiloxane segment-containing diblock macromolecular quaternary ammonium salt according to claim 7 or 8 for controlling rice sheath blight disease.
10. The use of the polysiloxane segment-containing diblock macromolecular quaternary ammonium salt according to claim 9 for controlling rice sheath blight disease, characterized in that: the two-block macromolecular quaternary ammonium salt containing the polysiloxane chain segment inhibits the germination of rhizoctonia solani sclerotium.
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