CN108641087A - A kind of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes and the preparation method and application thereof - Google Patents
A kind of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses two block macromolecular quaternary ammonium salts of a kind of segment containing polysiloxanes and the preparation method and application thereof.The preparation method includes the following steps：A kind of single-ended polysiloxanes for vinyl is synthesized first；By carrying out click-reaction with mercaptoethanol, the single-ended polysiloxanes for hydroxyl is synthesized；Then the polysiloxanes of one-ended hydroxy carries out reacting synthesis polysiloxanes macromole evocating agent with 2 bromine isobutyl acylbromides, then causes the polymerization that DMAPMA carries out ATRP；Finally reuse the two block macromolecular quaternary ammonium salts that benzyl chloride carries out quaternary ammonium compounds into the segment containing polysiloxanes.It is this with amphiphilic macromolecular quaternary ammonium salt to Rhizoctonia solani Kuhn sclerotium with good absorption and penetrating power, to have good inhibiting effect to the sprouting of sclerotium.
Description
Technical field
The invention belongs to the synthesis application field of high molecular material, more particularly to two blocks of a kind of segment containing polysiloxanes
Macromolecular quaternary ammonium salt and the preparation method and application thereof.
Background technology
Rhizoctonia solani Kuhn is also known as " moire disease ", and popular name " spends sufficient bar ", is distributed widely in rice major producing country of the world,
It is had become first of three major disease of rice in China.Rhizoctonia solani Kuhn is a kind of soil caused by Rhizoctonia solani Kuhn (R.solani)
Disease is passed, mainly passes through vegetative propagation.There are mainly two types of existence forms, i.e. mycelia and sclerotium in its natural state for the bacterium.
Cause rice sheath blight disease to endanger a serious major reason and is that " sclerotial germination forms mycelia-mycelia and infects host-for it
Mycelia assembles under the conditions of being forced to forms sclerotium " this Infection cycie.
What the prevention currently for rice sheath blight disease was mainly carried out around the mycelia for how killing Rhizoctonia solani Kuhn, such as
The use of jinggangmeisu, but to the killing of sclerotium then without good method.This is because the sclerotium of Rhizoctonia solani Kuhn be by
Double-layer structure forms, and internal layer is living cells, and outer layer is then a large amount of ghost (reference document 1：Teruyoshi Hashiba,
Shizuo Mogi,Developmental changes in sclerotia of rice sheath blight fungus,
Phytopathology,1975,65:159-162；Reference document 2：Peng Shao fur coats, Zeng Zhaorui, Zhang Zhi's light rice sheath blight diseases and its
Prevent the Shanghai [M] science tech publishing house, 1986.p165-167, p184-185).And small molecule pesticide is due to absorption property
It is insufficient so that it is difficult to be gathered in sclerotium surface and penetrate into inside sclerotium in turn.What this was resulted in is required for periodically every year
A large amount of pesticides are sprayed to rice field, prevent the harm brought after sclerotial germination.In addition, the pesticide of small molecule due to adsorptivity deficiency,
It is easy to be lost in together with the moisture of irrigation, causes that the sprinkling of large dosage is needed to make up the deficiency of its efficiency.
Invention content
Goal of the invention the shortcomings that being to overcome the prior art of the present invention with it is insufficient, a kind of segment containing polysiloxanes is provided
The preparation method of two block macromolecular quaternary ammonium salts.
Another object of the present invention is to provide two blocks of the segment containing polysiloxanes obtained by above-mentioned preparation method
Macromolecular quaternary ammonium salt.
Another object of the present invention also resides in the two block macromolecular quaternary ammonium salts for providing the segment containing polysiloxanes
Using.
The purpose of the invention is achieved by the following technical solution：A kind of two block macromolecular quaternary ammoniums of the segment containing polysiloxanes
The preparation method of salt, includes the following steps：
(1) synthesis of the dimethyl silicone polymer (PDMS-Vi) of single-ended vinyl：Hexamethyl is added in organic solvent A
Cyclotrisiloxane (D3), in an inert gas atmosphere, with n-BuLi initiated polymerization, it is eventually adding dimethyl ethenyl chlorine
Silane terminates polymerisation；To product purification obtained by the reaction, obtain transparent oily liquid product, i.e., poly- the two of single-ended vinyl
Methylsiloxane；
(2) synthesis of the dimethyl silicone polymer (PDMS-OH) of one-ended hydroxy：By organic solvent B, PDMS-Vi, sulfydryl second
Alcohol and catalyst mixing, obtain clear solution, pure to product obtained by the reaction with ultraviolet light-initiated Radical Addition
Change, obtains the dimethyl silicone polymer of one-ended hydroxy；
(3) single-ended dimethyl silicone polymer (PDMS-Br) synthesis with bromine：PDMS-OH and three is added in organic solvent C
Ethamine adds the mixed solution that 2- bromine isobutyl acylbromides are formed with organic solvent C, in an inert gas atmosphere hybrid reaction；It is right
Product purification obtained by the reaction obtains dimethyl silicone polymer of the end group with bromine；
(4) di-block copolymer (PDMS-b-PDMAEMA) of polysiloxanes and polymethylacrylic acid dimethylaminoethyl
Synthesis：By organic solvent D, PDMS-Br, dimethylaminoethyl methacrylate (DMAEMA), CuBr and N, N, N', N ", N "-five
Methyl diethylene triamine (PMDETA) mixes, and carries out polymerisation in an inert gas atmosphere, pure to product obtained by the reaction
Change, obtains light yellow viscous liquid product, the i.e. di-block copolymer of polysiloxanes and polymethylacrylic acid dimethylaminoethyl；
(5) synthesis of two block macromolecular quaternary ammonium salts (PDMS-b-QPDMAEMA) of the segment containing polysiloxanes：By PDMS-
B-PDMAEMA, benzyl chloride are dissolved in organic solvent E, react in an inert gas atmosphere, are purified to product, obtain containing poly- silicon
Two block macromolecular quaternary ammonium salts of oxygen alkane segment.
The above organic solvent A, B, C, D, E are for dissolving reactive material, itself does not participate in reaction.
The above inert gas is preferably nitrogen.
Organic solvent A described in step (1) is preferably tetrahydrofuran.
The volumetric usage of solution organic solvent A described in step (1) is preferably equivalent to hexamethyl cyclotrisiloxane list
1.5~4 times of (mL of weight：g)；More preferably 1.8~2 times.
N-BuLi, hexamethyl cyclotrisiloxane and dimethyl vinyl chlorosilane described in step (1) are in molar ratio
1：(13.5~134.9)：(1~1.2) it matches.
The condition of polymerisation described in step (1) is preferably 0~5 DEG C of 12~36h of polymerization.
The step of purifying described in step (1) is preferably：Solvent and small point unpolymerized is removed by vacuum distillation
Then sub- raw material is filtered to remove side product chlorinated lithium powder, obtain PDMS-Vi after purification.
Organic solvent B described in step (2) is preferably tetrahydrofuran.
The quality dosage of organic solvent B described in step (2) is preferably be equivalent to PDMS-Vi mass 1~4 times；More
Preferably 2~3 times.
Catalyst described in step (2) is dimethoxybenzoin.
PDMS-Vi and the mercaptoethanol described in step (2) in molar ratio 1:1 proportioning.
The dosage of catalyst described in step (2) preferably presses PDMS-Vi：Catalyst=mass ratio 1:0.02 proportioning meter
It calculates.
The condition of Radical Addition described in step (2) preferably reacts 30~90min at room temperature；Preferably 30
~60min.
The room temperature is 10~35 DEG C；More preferably 20~25 DEG C.
The ultraviolet light that ultraviolet light optimal wavelength described in step (2) is 350-365nm；More preferable wavelength is 365nm's
Ultraviolet light.
The step of purifying described in step (2), is preferably as follows：Solvent is removed by vacuum distillation, by gained thick liquid
With methanol extraction, unreacting material is removed, repeat 0 time or more, then vacuum distillation obtains PDMS-OH after purification.
The number of the repetition is preferably 2~3 times.
Organic solvent C described in step (3) is tetrahydrofuran.
The quality dosage of organic solvent C described in step (3) is preferably be equivalent to PDMS-OH mass 1.3~3 times；
More preferably 2~2.5 times.
PDMS-OH, triethylamine and 2- bromine isobutyl acylbromides described in step (3) in molar ratio 1：(1~1.2)：(1~
1.2) it matches.
The condition of reaction described in step (3) preferably reacts 1h at 0 DEG C, then reacts at room temperature for 24 hours.
The room temperature is 10~30 DEG C；More preferably 20~25 DEG C.
The step of purifying described in step (3), is preferably as follows：It is filtered to remove by-product ammonium salt powder, vacuum distillation removes
Solvent removes not anti-raw material using methanol extraction, repeat 0 time or more, it is then evaporated under reduced pressure, obtains PDMS-Br after purification.
The number of the repetition is preferably 2~3 times.
Organic solvent D described in step (4) is preferably isopropanol.
The dosage of organic solvent D described in step (4) is preferably 3~8 times of dimethylaminoethyl methacrylate quality；
More preferably 4~6 times.
PDMS-Br, dimethylaminoethyl methacrylate, CuBr and N described in step (4) ,-five first of N, N', N ", N "
Base diethylene triamine in molar ratio 1：18：(1~1.2)：(1~1.2) it matches.
The condition of reaction described in step (4) preferably reacts 5~20h at 40~80 DEG C；More preferably 45~
6~10h is reacted at 55 DEG C；Most preferably 8h is reacted at 50 DEG C.
The step of purifying described in step (4), is preferably as follows：Neutral alumina stirring is added until solution is become by green
To be colourless, then filtering powders away, and finally rotates out solvent and unreacted monomer, obtains PDMS-b- after purification
PDMAEMA。
Organic solvent E described in step (5) is preferably toluene and ethyl alcohol by quality 1:1 obtained mixed solution.
The volumetric usage of organic solvent E described in step (5) be preferably be equivalent to PDMS-b-PDMAEMA mass 2~
3 times.
PDMS-b-PDMAEMA and the benzyl chloride described in step (5) in molar ratio 1:18 proportionings.
The condition of reaction described in step (5) preferably reacts 16~32h at 60~80 DEG C；More preferably 65~
20~28h is reacted at 75 DEG C；Most preferably reacted for 24 hours at 70 DEG C.
Purifying preferred steps described in step (5) are：It is evaporated under reduced pressure out partial solvent, a large amount of anhydrous ethers are added by season
Ammonium salt, which separates out, to be come, and supernatant liquor is then outwelled, and is put into 50 DEG C of vacuum drying oven drying to get two blocks of the segment containing polysiloxanes
Macromolecular quaternary ammonium salt PDMS-b-QPDMAEMA.
By the rate of charge of D3 monomers and n-BuLi, polymerization reaction time in rate-determining steps (1), can be prepared not
PDMS is obtained with molecular weight, by the ingredient proportion of DMAEMA monomers and PDMS-Br in rate-determining steps (5), can be obtained different poly-
The PDMS-b-PDMAEMA of dimethylaminoethyl methacrylate chain length.
A kind of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes, are obtained by above-mentioned preparation method.
Two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes are preferably with the following characteristics containing poly- silica
Two block macromolecular quaternary ammonium salts of alkane segment：Polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl chain
The degree of polymerization ratio of section is PDMS：QPDMAEMA=(13~135):18, PDMS blocks grow 1~10kDa, and QPDMAEMA blocks are long
5kDa。
Application of the two block macromolecular quaternary ammonium salts of the above-mentioned segment containing polysiloxanes in preventing rice sheath blight disease is especially used
In the sprouting for inhibiting sclerotium.
The present invention has the following advantages and effects with respect to the prior art：
The present invention provides a kind of two block macromolecular quaternary ammonium salt (PDMS- with the amphiphilic segment containing polysiloxanes
B-QPDMAEMA preparation method).Compared with prior art, after first step D3 anion open loops, using dimethyl second
Alkenyl chlorosilane carries out the silicone oil that single-ended vinyl is made in sealing end, and can be accurately controlled by controlling the molar ratio of initiator and D3
The molecular weight of the silicone oil of single-ended vinyl.Secondly click-reaction is utilized, hydroxyl access macromolecular chain is obtained into end hydroxyl silicone oil, this
One step is efficiently convenient, and occurs without by-product, optimizes later Purification, greatly improves yield.Finally utilize
DMAPMA is accessed on PDMS the copolymer for forming two blocks by ATRP, has accurately controlled the molecular weight of PDMAEMA segments.Pass through essence
The really molecular weight of two blocks of regulation and control, finally obtains the amphiphilic macromolecular quaternary ammonium salt that ability is killed with good sclerotium.
Description of the drawings
Fig. 1 is the chemical reaction route map of Examples 1 to 6.
Fig. 2 is PDMS-Vi, PDMS-OH, PDMS-Br, PDMS-b-PDMAEMA and PDMS-b-QPDMAEMA of embodiment 1
IR Characterization figure and nuclear magnetic spectrogram.
Fig. 3 is the 1g/L that Rhizoctonia solani Kuhn sclerotium is soaked in that the PDMS-b-QPDMAEMA synthesized in Examples 1 to 6 is prepared
The schematic diagram of aqueous solution 1h front and rear surfaces contact angles variation.
Fig. 4 is the minimal inhibitory concentration of the PDMS-b-QPDMAEMA Rhizoctonia solani mycelia synthesized in Examples 1 to 6
(MIC) and minimum bactericidal concentration (MFC) schematic diagram.
Fig. 5 is the Germination suppression effect of the PDMS-b-QPDMAEMA Rhizoctonia solani sclerotium synthesized in Examples 1 to 6
Schematic diagram；5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC wherein in X-coordinate refer to be prepared by PDMS-b-QPDMAEMA
Aseptic aqueous solution concentration distinguishes it and corresponds to 5,10,15 and 20 times of minimal inhibitory concentration (MIC)；7D, 14D, 21D in Y coordinate,
28D and 35D refer to sclerotium impregnated in the aseptic aqueous solution prepared by PDMS-b-QPDMAEMA duration be respectively 7 days, 14 days, 21
It, 28 days and 35 days；Sclerotial germination inhibiting rate in Z coordinate refer to 40 sclerotium prepared by PDMS-b-QPDMAEMA it is sterile
The sclerotium number percent inactivated after being impregnated in aqueous solution.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Reagent used in the present invention is commercially available.
Embodiment 1
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=27:The long 2kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process is as shown in Figure 1, specific
Steps are as follows：
(1) in the Schlenk bottle equipped with magnetic stir bar, 50g D are added3, then sealed, will be taken out in bottle with silica gel plug
High pure nitrogen is passed through after vacuum, repetitive operation is three times to ensure to be full of nitrogen in bottle.Tetrahydrochysene furan is dried with syringe injection 100mL
Mutter dissolving D3After obtaining clear solution, the hexane solution 10mL of the n-BuLi containing 2.5mol/L is injected at 0 DEG C, cause it is cloudy from
Sub- ring-opening polymerisation.After being kept stirring about 12h at 0 DEG C, 3.02g dimethyl vinyl chlorosilanes is taken to be injected into Schlenk bottle,
Continue stir about 1h with complete termination to polymerize.After 120 DEG C of rotary evaporations of reaction solution are removed solvent and small molecule monomer, have a large amount of
Side product chlorinated lithium powder is precipitated, and the thick liquid product PDMS-Vi of water white transparency, infrared spectrum and nuclear-magnetism spectrum is obtained by filtration
Figure is respectively as shown in Fig. 2 (A), (B).
(2) in the suprasil flask equipped with magnetic stir bar, be added 40g PDMS-Vi, 1.57g mercaptoethanols and
0.8g dimethoxybenzoins；80.0g tetrahydrofuran above-mentioned raw materials are added and form colourless transparent solution.In the ultraviolet of 365nm wavelength
Under light irradiation, it is kept stirring reaction 60min.After reaction was completed, decompression steam solvent, obtain thick liquid crude product, by its with
Methanol mixes, and is fully shaken up in separatory funnel, static to take lower liquid, in triplicate.Finally vacuum distillation removes remaining
Methanol obtains the product liquid PDMS-OH of colorless viscous, and infrared spectrum and nuclear magnetic spectrogram are respectively as Fig. 2 (A), (B) are shown.
(3) in the glass flask equipped with magnetic stir bar, 30g PDMS-OH, triethylamine 1.52g is added, with 40g tetrahydrochysenes
Furans dissolves, and takes 2- bromine isobutyl acylbromides 3.45g to be dissolved in 20g tetrahydrofurans and is placed in titration funnel, and with the speed of 1 drop/5s
It instills in flask and reacts 1h at 0 DEG C, then react at normal temperatures for 24 hours.After reaction was completed, filters and be evaporated under reduced pressure removing tetrahydrochysene
Crude product is mixed with methanol, is fully shaken up in separatory funnel by furans, static to take lower liquid, in triplicate, finally subtract
Residual methanol is distilled off in pressure, obtains final product PDMS-Br, infrared spectrum and nuclear magnetic spectrogram are respectively such as Fig. 2 (A), (B) institute
Show.
(4) 0.62g CuBr are added in the Schlenk bottle equipped with magnetic stir bar, the stirring of 50mL glacial acetic acid is then added
15min outwells liquid, retains powder, so in triplicate；Then 50mL absolute ethyl alcohol and stirring 10min are added, outwell liquid,
Retain powder, so in triplicate；It is eventually adding 7.22g PDMS-Br, 10g DMAEMA, 0.68g PMDETA, 45g isopropanols
It in flask, is sealed with silica gel plug, high pure nitrogen is passed through after being vacuumized in bottle, repetitive operation is three times to ensure to be full of nitrogen in bottle
Gas reacts 8h at 50 DEG C.After reaction, isopropanol is fallen in vacuum distillation, and 100mL acetone solutions are added.Then it is added a large amount of
Neutral alumina is become colorless up to solution by green, filters out solid powder, the liquid pressure-reducing being collected into is distilled off third
Ketone obtains final product PDMS-b-PDMAEMA, and infrared spectrum and nuclear magnetic spectrogram are respectively as Fig. 2 (A), (B) are shown.
(5) in three mouthfuls of glass flasks equipped with magnetic stir bar be added 10g PDMS-b-PDMAEMA mixed with 20mL it is molten
Liquid (toluene and ethyl alcohol by volume 1:1 is mixed to get), 4.68g benzyl chlorides are added, condensing reflux at nitrogen, then 70 DEG C is passed through
Reaction is for 24 hours.After having reacted, it is evaporated under reduced pressure out a part of methanol, a large amount of ether is then added, solid is precipitated, after standing a period of time
Most of supernatant is outwelled, is put into vacuum drying oven drying to get quaternary ammonium salt PDMS-b-QPDMAEMA, and referred to as S2Q5。
Embodiment 2
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=40:The long 3kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process is as shown in Figure 1, with reality
The step of applying example 1 is roughly the same, differs only in：
The injection volume of n-BuLi is 6.67mL in step (1), and the time being kept stirring at 0 DEG C is about 18h, dimethyl
The inventory of vinyl chlorosilane is 2.01g；
The inventory of mercaptoethanol is 1.04g in step (2)；
The inventory of triethylamine and 2- bromine isobutyl acylbromides is respectively 1.01g and 2.30g in step (3)；
The inventory of PDMS-Br is 10.83g in step (4)；
The inventory of benzyl chloride is 3.87g in step (5).
Products therefrom is referred to as S3Q5。
Embodiment 3
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=54:The long 4kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process is as shown in Figure 1, with reality
The step of applying example 1 is roughly the same, differs only in：
The injection volume of n-BuLi is 5.00mL in step (1), and the time being kept stirring at 0 DEG C is about dimethyl for 24 hours
The inventory of vinyl chlorosilane is 1.51g；
The inventory of mercaptoethanol is 0.78g in step (2)；
The inventory of triethylamine and 2- bromine isobutyl acylbromides is respectively 0.76g and 1.73g in step (3)；
The inventory of PDMS-Br is 14.44g in step (4)；
The inventory of benzyl chloride is 3.30g in step (5)；
Products therefrom is referred to as S4Q5。
Embodiment 4
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=67:The long 5kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process is as shown in Figure 1, with reality
The step of applying example 1 is roughly the same, differs only in：
The injection volume of n-BuLi is 4.00mL in step (1), and the time being kept stirring at 0 DEG C is about 30h, dimethyl
The inventory of vinyl chlorosilane is 1.21g；
The inventory of mercaptoethanol is 0.63g in step (2)；
The inventory of triethylamine and 2- bromine isobutyl acylbromides is respectively 0.61g and 1.38g in step (3)；
The inventory of PDMS-Br is 18.05g in step (4)；
The inventory of benzyl chloride is 2.87g in step (5)；
Products therefrom is referred to as S5Q5。
Embodiment 5
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=108:The long 8kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process as shown in Figure 1, with
The step of embodiment 1, is roughly the same, differs only in：
The injection volume of n-BuLi is 2.50mL in step (1), and the time being kept stirring at 0 DEG C is about 36h, dimethyl
The inventory of vinyl chlorosilane is 0.76g；
The inventory of mercaptoethanol is 0.39g in step (2)；
The inventory of triethylamine and 2- bromine isobutyl acylbromides is respectively 0.38g and 0.87g in step (3)；
The inventory of PDMS-Br is 28.88g in step (4)；
The inventory of benzyl chloride is 2.07g in step (5)；
Products therefrom is referred to as S8Q5。
Embodiment 6
The preparation of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：
The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=135:The long 10kDa of 18, PDMS blocks, the long 5kDa of QPDMAEMA blocks.Preparation process as shown in Figure 1,
The step of with embodiment 1, is roughly the same, differs only in：
The injection volume of n-BuLi is 2.00mL in step (1), and the time being kept stirring at 0 DEG C is about 36h, dimethyl
The inventory of vinyl chlorosilane is 0.61g；
The inventory of mercaptoethanol is 0.32g in step (2)；
The inventory of triethylamine and 2- bromine isobutyl acylbromides is respectively 0.31g and 0.69g in step (3)；
The inventory of PDMS-Br is 36.10g in step (4)；
The inventory of benzyl chloride is 1.75g in step (5)；
Products therefrom is referred to as S10Q5。
Effect example
No. 119 bacterial strains of Rhizoctonia solani Kuhn (R.solani AG-1-IA) are resource environment institute of Agricultural University Of South China plant
Department of pathology's fungal studies room provides, and is to detach to obtain from the rice disease leaf sheath for showing apparent banded sclerotial blight symptom, pathogenicity compared with
By force, be Guangzhou province dominant strain (document " Zhou Erxun, Yang Mei, Li Lin, wait culture mediums to Rhizoctonia solani Kuhn mycelia give birth to
Long and Sclerotia forming influence [J] Agricultural University Of South China journal, 2002,23 (3):It is disclosed in 33-35. ").In the lab,
By 28 DEG C of incubators, PDA culture medium culture is simultaneously 7~14 days ripe, obtains ripe sclerotium.
One, following performance detection is carried out to above-described embodiment 1~6：
(1) Rhizoctonia solani sclerotium adsorption capacity is tested
It uses ultra-pure water as solution first, is tested using optical contact angular measurement analyzer (DropMeter A-100)
The contact angle on sclerotium surface, the quaternary ammonium salt aqueous solution (quaternary ammonium salt polymerization prepared by Examples 1 to 6 that then compound concentration is 1g/L
Object), sclerotium is impregnated into 1h in quaternary ammonium salt aqueous solution, sclerotium is taken out and with the slight rinse of ultra-pure water, surveys again after natural drying
The contact angle for trying sclerotium surface, two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes are judged by the decline degree of contact angle
To the adsorbance of sclerotium.
(2) the fungistatic effect test of Rhizoctonia solani mycelia
The appropriate mycelia of picking from potato dextrose medium (PD culture mediums) uses PD after being ground with 1mL homogenizers
Dilution, is used in combination blood counting chamber to count, controls the concentration of bacteria suspension 105~106Within the scope of CFU/mL.Take appropriate quaternary ammonium salt poly-
Object is closed, PD fluid nutrient mediums are added, by polymer dilution at a series of concentration with gradient.And prepared polymer is mixed
It closes liquid to sequentially add in tissue culture plate (96 hole) according to the sequence of high concentration to low concentration, 100 μ L polymerizations is added in every hole
Object solution, and 100 μ L bacteria suspensions are added, blow and beat mixing.The PD or dilute of same volume is respectively only added in separately two groups of controls of setting
Release one times of bacteria suspension；Each processing is at least repeated 3 times.2d is cultivated under 28 DEG C of constant temperature.After tissue culture plate culture 2d, in every
50 μ L 5%TTC dyestuffs, mixing is added in hole, and is protected from light in 28 DEG C of biochemical cultivation cases and is incubated 2h, (i.e. not aobvious red with not long bacterium
Color) minimum polymer concentration as MIC.After measuring MIC experiments, since MIC is to polymer high concentration direction, respectively take
100 μ L are seeded in respectively in blank potato glucose solid medium tablets (PDA plate), and about 4-5 concentration uses spreader
It gently pushes open, 2d is cultivated in 28 DEG C of constant incubators, whether there is or not thalli growths for observation, with clump count in tablet culture less than 5
Polymer concentration is as MFC.
(3) the Germination suppression measure of merit of Rhizoctonia solani sclerotium
It weighs appropriate quaternary ammonium salt PDMS-b-QPDMAEMA to sterilize in the UV lamp after 20min, be diluted to respectively with sterile water
5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC, and it is settled to 40mL, compare the sterile water for same volume.It will be dry
Sclerotium is soaked in the quaternary ammonium salt solution of above-mentioned various concentration, and 200 sclerotium are impregnated in each processing, are placed at 8 DEG C and are incubated 35d.
Every 7d, each handles 40 sclerotium of random picking and carry out sclerotial germination experiment.It is respectively 5 × MIC, 10 to prepare quaternary ammonium salinity
The PDA plate of × MIC, 15 × MIC and 20 × MIC, sclerotium is moved on tablet, and 10 sclerotium of each tablet each handle four
A repetition.It is placed at 28 DEG C after cultivating 1d, statistics of taking pictures Germination suppression rate, and picking does not sprout sclerotium and carries out slice sprouting in fact
It tests.Sclerotium is cut into four with sterilized blade, and moves to a concentration of 5 × MIC, 10 × MIC, 15 × MIC and 20 × MIC
On tablet, 28 DEG C, 2d is cultivated, counts 4 sclerotium numbers that all do not sprout.
(4) to the toxotest of silkworm and kunming mice.
Reference《Criterion is tested in GB/T 31270.11-2014 chemical pesticide environmental safety assessments --- and the 11st：Silkworm is anxious
Property toxicity test》, using leaf dipping method toxicity test, concrete operations are as follows：Select silkworm from 2 ages, each drug be arranged 5 it is dense
Degree, and blank control is set, control group is parallel with the setting 3 of each concentration.Every group of 20 boss silkworms, are respectively placed in 90mm culture mediums
In.It is configured to the liquid of various concentration using weight method, goes arteries and veins mulberry leaf to be immersed in 10s (control group mulberries in 10mL liquids 1.0g
Leaf is handled with deionized water), silkworm is fed after drying, is fed twice within one day, and moderate in culture dish edge one block size of placement
Absorbent cotton keep humidity.Observe and record for 24 hours, the death toll and poisoning symptom of the tested silkworm of 48h, 72h and 96h.It utilizes
SPSS handles data, finds out virulence regression equation and half lethal concentration (LC50) of the different quaternary ammonium salt of three classes to silkworm.
Reference《GB 15193.3-2014 national food safety standard acute oral toxicity tests》, using oral administration by gavage,
Before experiment, test mice 4~6h of fasting, free water.Concrete operation method is as follows：Mouse is divided into 6 groups, it is every group 10 small
After weighing, the gavage amount of three classes different structure quaternary ammonium salt is determined by mouse weight for mouse, the oral gavage same volume of control group
PBS.Fasting 1h~2h after gavage is observed without feeding after apparent problem, and is observed in 48h and 14d, the state of mouse, weight and
Diet situation, and count the death condition of mouse under each processing group.Using AOT425 software data processings, three classes difference is found out
The quaternary ammonium salt of structure measures (LD50) and its confidence interval to the median lethal of mouse.
Two, testing result
As a result as shown in Fig. 3~5 and table 1.
The contact angle that sclerotium surface after the aqueous solution of quaternary ammonium salt PDMS-b-QPDMAEMA was impregnated in Fig. 3 has different journeys
The decline of degree illustrates that quaternary ammonium salt PDMS-b-QPDMAEMA stabilizations have been adsorbed on sclerotium surface, and works as polysiloxane chain segment molecule
Suctions of the quaternary ammonium salt PDMS-b-QPDMAEMA (QAS polymer prepared by embodiment 3 and 4) to sclerotium when amount is 4000 and 5000
Attached amount is maximum.Fig. 4 indicates the minimal inhibitory concentration (MIC) and most of quaternary ammonium salt PDMS-b-QPDMAEMA Rhizoctonia solani mycelia
Small bacteriocidal concentration (MFC) is 40 μ g/mL substantially, and fungistatic effect is preferable.
Fig. 5 indicates that quaternary ammonium salt PDMS-b-QPDMAEMA Rhizoctonia solani sclerotium bacterias have the effect of Inhibiting germination, and works as
(QAS polymer prepared by embodiment 4) effect reaches best when siloxanes chain segment molecular weight is 5000.
Quaternary ammonium salt PDMS-b-QPDMAEMA is all higher than 2000mg/L to the half lethal concentration (LC50) of silkworm in table 1, says
Bright quaternary ammonium salt PDMS-b-QPDMAEMA shows as silkworm nontoxic；Median lethal meters of the PDMS-b-QPDMAEMA to kunming mice
Amount (LD50) is all higher than 2000mg/L, shows as approaching practical nontoxic.
Table 1
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of two block macromolecular quaternary ammonium salts of segment containing polysiloxanes, it is characterised in that including walking as follows
Suddenly：
(1) synthesis of the dimethyl silicone polymer of single-ended vinyl：Hexamethyl cyclotrisiloxane is added in organic solvent A,
In inert gas atmosphere, with n-BuLi initiated polymerization, it is eventually adding dimethyl vinyl chlorosilane and terminates polymerisation；
To product purification obtained by the reaction, transparent oily liquid product, i.e., the dimethyl silicone polymer of single-ended vinyl are obtained；
(2) synthesis of the dimethyl silicone polymer of one-ended hydroxy：By organic solvent B, single-ended vinyl dimethyl silicone polymer,
Mercaptoethanol and catalyst mixing, obtain clear solution, with ultraviolet light-initiated Radical Addition, to production obtained by the reaction
Object purifies, and obtains the dimethyl silicone polymer of one-ended hydroxy；
(3) the single-ended dimethyl silicone polymer synthesis with bromine：The dimethyl silicone polymer of one-ended hydroxy is added in organic solvent C
And triethylamine, the mixed solution that 2- bromine isobutyl acylbromides are formed with organic solvent C is added, mixing is anti-in an inert gas atmosphere
It answers；To product purification obtained by the reaction, dimethyl silicone polymer of the end group with bromine is obtained；
(4) synthesis of the di-block copolymer of polysiloxanes and polymethylacrylic acid dimethylaminoethyl：By organic solvent D, end
Dimethyl silicone polymer, dimethylaminoethyl methacrylate, CuBr and the N of base band bromine, N, N', N ", N "-pentamethyl divinyls
Base triamine mixes, and carries out polymerisation in an inert gas atmosphere, to product purification obtained by the reaction, obtains faint yellow viscous fluid
Body product is the di-block copolymer of polysiloxanes and polymethylacrylic acid dimethylaminoethyl；
(5) synthesis of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes：By polysiloxanes and polymethylacrylic acid diformazan
Di-block copolymer, the benzyl chloride of amino ethyl ester are dissolved in organic solvent E, react in an inert gas atmosphere, are carried out to product pure
Change, obtains two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes.
2. the preparation method of two block macromolecular quaternary ammonium salts of the segment according to claim 1 containing polysiloxanes, feature
It is：
N-BuLi, hexamethyl cyclotrisiloxane and dimethyl vinyl chlorosilane described in step (1) in molar ratio 1：
(13.5~134.9)：(1~1.2) it matches；
The dimethyl silicone polymer and the mercaptoethanol of single-ended vinyl described in step (2) in molar ratio 1:1 proportioning；
Dimethyl silicone polymer, triethylamine and the 2- bromine isobutyl acylbromides of one-ended hydroxy described in step (3) in molar ratio 1：(1
~1.2)：(1~1.2) it matches；
Dimethyl silicone polymer of the end group with bromine, dimethylaminoethyl methacrylate, CuBr described in step (4) and N, N,
N', N ", N "-pentamethyldivinyltriamine in molar ratio 1：18：(1~1.2)：(1~1.2) it matches；
Di-block copolymer and the chlorine of the polysiloxanes with polymethylacrylic acid dimethylaminoethyl described in step (5)
Change benzyl in molar ratio 1:18 proportionings.
3. the preparation method of two block macromolecular quaternary ammonium salts of the segment according to claim 1 containing polysiloxanes, feature
It is：
Organic solvent A described in step (1) is tetrahydrofuran；
Organic solvent B described in step (2) is tetrahydrofuran；
Catalyst described in step (2) is dimethoxybenzoin；
Organic solvent C described in step (3) is tetrahydrofuran；
Organic solvent D described in step (4) is isopropanol；
Organic solvent E described in step (5) is that toluene presses quality 1 with ethyl alcohol:1 obtained mixed solution.
4. the preparation method of two block macromolecular quaternary ammonium salts of the segment according to claim 1 containing polysiloxanes, feature
It is：
The volumetric usage of solution organic solvent A described in step (1) is equivalent to the 1.5 of hexamethyl cyclotrisiloxane monomer mass
~4 times；
The quality dosage of organic solvent B described in step (2) is equivalent to the 1 of the dimethyl silicone polymer quality of single-ended vinyl
~4 times；
The dosage of catalyst described in step (2) presses the dimethyl silicone polymer of single-ended vinyl：Catalyst=mass ratio 1:
0.02 proportioning calculates；
The quality dosage of organic solvent C described in step (3) is equivalent to the 1.3 of the dimethyl silicone polymer quality of one-ended hydroxy
~3 times；
The dosage of organic solvent D described in step (4) is 3~8 times of dimethylaminoethyl methacrylate quality；
The volumetric usage of organic solvent E described in step (5) is equivalent to polysiloxanes and polymethylacrylic acid dimethylamino second
2~3 times of the di-block copolymer quality of ester.
5. the preparation method of two block macromolecular quaternary ammonium salts of the segment according to claim 1 containing polysiloxanes, feature
It is：
The condition of polymerisation described in step (1) is 0~5 DEG C of 12~36h of polymerization；
The condition of Radical Addition described in step (2) is to react 30~90min at room temperature；
Ultraviolet light described in step (2) is the ultraviolet light that wavelength is 350-365nm；
The condition of reaction described in step (3) is that 1h is reacted at 0 DEG C, is then reacted at room temperature for 24 hours；
The condition of reaction described in step (4) is that 5~20h is reacted at 40~80 DEG C；
The condition of reaction described in step (5) is that 16~32h is reacted at 60~80 DEG C.
6. the preparation method of two block macromolecular quaternary ammonium salts of the segment according to claim 1 containing polysiloxanes, feature
It is：
The step of purifying described in step (1) is：Solvent and unpolymerized small-molecule starting material are removed by vacuum distillation, so
After be filtered to remove side product chlorinated lithium powder, obtain the dimethyl silicone polymer of single-ended vinyl after purification；
The step of purifying described in step (2), is as follows：Solvent is removed by vacuum distillation, gained thick liquid methanol is extracted
It takes, removes unreacting material, repeat 0 time or more, then vacuum distillation obtains the polydimethylsiloxanes of one-ended hydroxy after purification
Alkane；
The step of purifying described in step (3), is as follows：It is filtered to remove by-product ammonium salt powder, vacuum distillation removes solvent, makes
With methanol extraction, not anti-raw material is removed, repeat 0 time or more, it is then evaporated under reduced pressure, obtains the single-ended poly- diformazan with bromine after purification
Radical siloxane；
The step of purifying described in step (4), is as follows：Neutral alumina stirring is added until solution is become colorless by green, so
Filtering powders away afterwards, finally rotates out solvent and unreacted monomer, obtains polysiloxanes after purification and polymethylacrylic acid
The di-block copolymer of dimethylaminoethyl；
The step of purifying described in step (5) is：It is evaporated under reduced pressure out partial solvent, a large amount of anhydrous ethers is added, quaternary ammonium salt sinks
It separates out, then outwells supernatant liquor, be put into 50 DEG C of vacuum drying oven drying to get two block macromoleculars of the segment containing polysiloxanes
Quaternary ammonium salt.
7. a kind of two block macromolecular quaternary ammonium salts of segment containing polysiloxanes, it is characterised in that：It is any by claim 1~6
Preparation method described in obtains.
8. two block macromolecular quaternary ammonium salts of the segment according to claim 7 containing polysiloxanes, it is characterised in that：Described
Two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes are that two blocks of the segment with the following characteristics containing polysiloxanes divide greatly
Sub- quaternary ammonium salt：The degree of polymerization ratio of polysiloxane block segment and quaternized polymethylacrylic acid dimethylaminoethyl segment is
PDMS：QPDMAEMA=(13~135):18, PDMS blocks grow 1~10kDa, the long 5kDa of QPDMAEMA blocks.
9. two block macromolecular quaternary ammonium salts of claim 7 or 8 segments containing polysiloxanes are in preventing rice sheath blight disease
Using.
10. two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes are in preventing rice sheath blight disease according to claim 9
Application, it is characterised in that：Two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes inhibit rice sheath blight disease sclerotium
It sprouts.
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| CN114057924A (en) * | 2020-08-04 | 2022-02-18 | 华南理工大学 | Main chain type macromolecular quaternary ammonium salt and preparation method and application thereof |
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