CN105901013A - Application of block macromolecule quaternary ammonium salt in growth inhibition of banana oxysporum - Google Patents
Application of block macromolecule quaternary ammonium salt in growth inhibition of banana oxysporum Download PDFInfo
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- CN105901013A CN105901013A CN201610278195.5A CN201610278195A CN105901013A CN 105901013 A CN105901013 A CN 105901013A CN 201610278195 A CN201610278195 A CN 201610278195A CN 105901013 A CN105901013 A CN 105901013A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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Abstract
The invention discloses application of block macromolecule quaternary ammonium salt in growth inhibition of banana oxysporum. The structural formula of the block macromolecule quaternary ammonium salt is shown as A. The block macromolecule quaternary ammonium salt can be well adhered to the surface of a hydrophobic material, so that growth of the banana oxysporum can be inhibited in liquor, and the banana oxysporum can be prevented and cured effectively on the surface of the hydrophobic material.
Description
Technical field
The invention belongs to the plant protection applied technical field of functional polymer, particularly to block macromole season
Ammonium salt purposes in suppression banana blight bacteria growing.
Background technology
Banana blight, is commonly called as Fructus Musae yellowtop or Panama disease, and this disease is to be infected banana plant dimension by one
Fungus Fusarium oxysporum Cuba's specialized form (Fusarium oxysporium f.sp.cubense) of tube bank is drawn
The soil-borne disease risen.Banana blight bacteria can make diseased plant wilting after infecting Fructus Musae and vascular bundle variable color is rotted,
Plant can be produced destructive injury.Therefore, this disease becomes International Plant quarantine object.
Banana blight can be allocated and transported by Fructus Musae seedling, soil and the agricultural machinery and implement etc. carried disease germs and be moved and carry out far
Propagation；Closely spread by water, the conidium carried disease germs.And the cause of disease of banana blight
Bacterium inside soil can remaining more than 30 years, do not have any pesticide can go it eradicate fall.At high temperature
Rainy, soil acidity, sandy loam, fertility are low, the glutinous weight of soil property, impeded drainage, subsoil poor permeability and
Farming is hindered under the effect of the factors such as root, and banana blight evil can be made again to occur.
For the preventing and treating of banana blight, there is domestic scholars that commercially available various medicaments is screened, but
Currently without a kind of highly desirable medicament.The most only diazosulfide is in the preventing and treating side to banana blight bacteria
There is certain effect in face.But still it is unsatisfactory for the needs of actual application, need exploitation to environment more environmental protection, to perfume (or spice)
The more preferable preparation of any of several broadleaf plants wilt prevention effect.
Summary of the invention
It is an object of the invention to the shortcoming overcoming prior art with not enough, it is provided that block macromole quaternary ammonium salt exists
Purposes in suppression banana blight bacteria growing.
The purpose of the present invention is achieved through the following technical solutions: block macromole quaternary ammonium salt is withered at suppression Fructus Musae
Purposes in pathogen growth.
The structural formula of described block macromole quaternary ammonium salt (PDMS-b-(PDMS-g-QAS)-b-PDMS) is such as
Shown in formula A:
Described R is preferably
The value of described m and described n determines according to molecular weight and percent grafting.
The value of described m is preferably 4～16；The value of described n is preferably 8～48；M, n are 4
Multiple.
The number-average molecular weight of the described polysiloxane backbone in block macromole quaternary ammonium salt is 2 × 103～1 × 104。
The chain number being grafted quaternary ammonium salt group in described block macromole quaternary ammonium salt accounts for the grafting total chain number of segment
The 1/3～1/8 of (percent grafting)；
Described block macromole quaternary ammonium salt is preferably made by the steps and obtains:
Double (the 3-aminopropyl)-1 of (1) 1,3-, 1,3,3-tetramethyl disiloxane (BAPTMDS,
1,3-BIS (3-AMINOPROPYL) TETRAMETHYLDISILOXANE) in the protection of primary amino radical:
Phthalic anhydride and double (3-aminopropyl)-1,1,3,3-tetramethyl two silica of 1,3-is added in organic solvent A
Alkane, reaction；The product purification obtaining reaction, obtains the end socket after being protected by phthalic anhydride (PA)
(BAPTMDS-PA2)；
(2) synthesis of hydrogen containing siloxane: with BAPTMDS-PA2, octamethylcy-clotetrasiloxane (D4)
And tetramethyl-ring tetrasiloxane (D4 H) it is raw material, with sulfuric acid solution as catalyst, anti-in organic solvent B
Should；The product purification obtaining reaction, obtains hydrogen containing siloxane (PA-PDMS-co-PHMS-PA)；
(3) synthesis of tertiary amine groups polysiloxanes: under an inert atmosphere, toward containing that step (2) prepares
Hydrogen polysiloxanes adds DMAA (DMAA), reacts under catalyst action；To reaction
The product purification obtained, obtains tertiary amine groups polysiloxanes (PA2-PDMS-g-DMAA)；
(4) deprotection of the Amino End Group of tertiary amine groups polysiloxanes: add step (3) in organic solvent C
The tertiary amine groups polysiloxanes prepared and a hydrazine hydrate, reaction；The product purification obtaining reaction, obtains
Slough the tertiary amine groups polysiloxanes with Amino End Group of phthalic anhydride protection
((NH2)2-PDMS-g-DMAA)；
(5) synthesis of single-ended hydrogen containing siloxane: under an inert atmosphere, adds pregnancy in organic solvent D
Basic ring trisiloxanes (D3) and n-butyllithium solution, reaction；It is subsequently added into dimethylchlorosilane and terminates reaction,
The product purification obtaining reaction, obtains single-ended hydrogen containing siloxane (PDMS-H)；
(6) synthesis of single-ended ester group polysiloxanes: under an inert atmosphere, prepared by past step (5) single-ended
Hydrogen containing siloxane adds Tert-butyl Methacrylate (tBMA), reacts under catalyst action；To instead
The product purification that should obtain, obtains single-ended ester group polysiloxanes (PDMS-tBMA)；
(7) synthesis of single-ended carboxyl polysiloxanes: in single-ended ester group polysiloxanes prepared by step (6)
Add concentrated sulphuric acid, reaction；The product purification obtaining reaction, obtains single-ended carboxyl polysiloxanes
(PDMS-COOH)；
(8) synthesis of polysiloxane block copolymers: add prepared by step (7) in organic solvent E
The tertiary amine groups polysiloxanes with Amino End Group that single-ended carboxyl polysiloxanes and step (4) prepare, is urging
React under agent effect；The product purification obtaining reaction, obtains tertiary amine groups polysiloxane block copolymers
(PDMS-b-(PDMS-g-DMAA)-b-PDMS)；
(9) synthesis of the polysiloxane block copolymers containing quaternary ammonium salt group: under an inert atmosphere, toward organic
Solvent F adds tertiary amine groups polysiloxane block copolymers and halogenated hydrocarbons, reaction；The product that reaction is obtained
Purification, obtains the polysiloxane block copolymers containing quaternary ammonium salt group
(PDMS-b-(PDMS-g-QAS)-b-PDMS)。
The above organic solvent A, B, C, D, E, F are for dissolving reacting substance, and itself is not
Participate in reaction.Organic solvent A, B, C, D, E, F can be identical materials, it is also possible to be different
Material.
The above inert atmosphere is preferably nitrogen atmosphere.
Double (3-the aminopropyl)-1,1,3,3-tetramethyl disiloxane of 1,3-described in step (1) is with described
Phthalic anhydride 1:(2.2 in molar ratio～2.6) proportioning.
Organic solvent A described in step (1) be preferably in oxolane and chloroform one or both.
It is double (3-aminopropyl) that the quality consumption of the organic solvent A described in step (1) is preferably 1,3-
2 times of-1,1,3,3-tetramethyl disiloxane+phthalic anhydride gross mass.
The condition of the reaction described in step (1) is preferably reacts 4～6h in 60～80 DEG C.
The step of the purification described in step (1) is preferably as follows: organic solvent A is distilled off by decompression,
Use chloroform lysate, with 55～65 DEG C of hot wash products, take chloroform layer decompression distillation, obtain after purification
The end socket (BAPTMDS-PA protected by phthalic anhydride2)。
The number of times of described washing is preferably 3～5 times.
Tetramethyl-ring tetrasiloxane described in step (2), described octamethylcy-clotetrasiloxane are with described
BAPTMDS-PA22.81～6:11.24～13.29:1 proportioning in molar ratio.
The sulfuric acid solution that sulfuric acid solution preferably concentration is 80～90wt% described in step (2)；More preferably
It it is the sulfuric acid solution of 80～86wt%.
The quality consumption of the sulfuric acid solution described in step (2) is equivalent to octamethylcy-clotetrasiloxane+tetramethyl
The 2～4% of ring four silica gross mass；More preferably 2～3%.
Organic solvent B described in step (2) be preferably in chloroform and toluene one or both.
The quality consumption of the organic solvent B described in step (2) is BAPTMDS-PA2+ prestox ring four
The gross mass of siloxanes+tetramethyl-ring tetrasiloxane.
Reaction described in step (2) is preferably reacts 12～14h at 25～30 DEG C.
The step of the purification described in step (2) is specific as follows: use sodium bicarbonate aqueous solution neutralisation of sulphuric acid, quiet
Postpone and take chloroform layer decompression distillation, obtain hydrogen containing siloxane (PA-PDMS-co-PHMS-PA) after purification.
The condition of described decompression distillation is preferably 150 DEG C of decompression distillations 4 hours.
The number-average molecular weight of the hydrogen containing siloxane described in step (2) is between 2 × 103～1 × 104Between.
Catalyst described in step (3) is Karstedt ' s catalyst.
Hydrogen containing siloxane described in step (3) and described DMAA press hydrogen containing siloxane
Middle hydrogen group and DMAA mol ratio are 1:(2～4) proportioning.
Catalyst described in step (3) is catalytic amount.
Described catalytic amount is preferably the Karstedt ' s of corresponding about 5～10 micrograms of every gram of hydrogen containing siloxane and urges
Agent.
The condition of the reaction described in step (3) is preferably reacts 48～72h in 80～100 DEG C.
The step of the purification described in step (3) is preferably as follows: decompression is distilled off the dimethallyl of excess
Base amine, obtains tertiary amine groups polysiloxanes (PA after purification2-PDMS-g-DMAA)。
Tertiary amine groups polysiloxanes described in step (4) and described hydrazine hydrate 1:(4.5 in molar ratio～
5.5) proportioning.
Organic solvent C described in step (4) be preferably in dehydrated alcohol and methanol one or both, excellent
Elect dehydrated alcohol as.
The quality consumption of the organic solvent C described in step (4) is preferably tertiary amine groups polysiloxanes+hydration
2 times of hydrazine gross mass.
The condition of the reaction described in step (4) is preferably reacts 10～14h in 75～85 DEG C.
The step of the purification described in step (4) is preferably as follows: decompression be distilled off organic solvent C, water and
One hydrazine hydrate, uses chloroform lysate, 55～65 DEG C of water washings, takes chloroform layer decompression distillation, obtain purification
After tertiary amine groups the polysiloxanes ((NH with Amino End Group2)2-PDMS-g-DMAA)。
The number of times of described washing is preferably 3～5 times.
Organic solvent D described in step (5) be preferably in oxolane and chloroform one or both.
The quality consumption of the organic solvent D described in step (5) is preferably equivalent to n-BuLi+hexamethyl
Cyclotrisiloxane+dimethylchlorosilane gross mass.
N-BuLi, hexamethyl cyclotrisiloxane and dimethylchlorosilane described in step (5) are in molar ratio
For 1:(4.5～22.5): 1 proportioning；It is preferably 1:4.5:1 proportioning in molar ratio.
The condition of the reaction described in step (5) is preferably reacts 20～24h in 0～10 DEG C.
The condition terminating reaction described in step (5) is preferably in 0～10 DEG C of stirring reaction 1～2h.
Purification described in step (5) specifically comprise the following steps that sucking filtration, decompression distillation, obtain after purification
Single-ended hydrogen containing siloxane (PDMS-H).
The number-average molecular weight of the single-ended hydrogen containing siloxane described in step (5) is between 1 × 103～5 × 103It
Between.
Catalyst described in step (6) is preferably chloroplatinic acid catalyst.
Described catalyst is catalytic amount
Described catalytic amount is preferably the chloroplatinic acid of corresponding about 5～10 micrograms of every gram of hydrogen containing siloxane.
Single-ended hydrogen containing siloxane described in step (6) is with described Tert-butyl Methacrylate in molar ratio
For 1:(1.2～1.4) proportioning.
The condition of the reaction described in step (6) is preferably reacts 12～14h in 75～85 DEG C；More preferably in
75～80 DEG C of reactions 12～14h.
Purification described in step (6) specifically comprise the following steps that sucking filtration, decompression distillation, obtain after purification
Single-ended ester group polysiloxanes (PDMS-tBMA).
Concentrated sulphuric acid described in step (7) be concentration be the sulphuric acid of 98wt%.
The quality consumption of the concentrated sulphuric acid described in step (7) is described single-ended ester group polysiloxanes quality
0.8～1%.
The condition of the reaction described in step (7) is preferably reacts 3～4h in 80～90 DEG C.
Chloroform lysate is used in specifically comprising the following steps that of purification described in step (7), then uses deionized water
Wash to water layer pH less than 8, take chloroform layer decompression distillation, obtain single-ended carboxyl polysiloxanes after purification
(PDMS-COOH)。
Each consumption of described deionized water is equivalent to chloroform stereometer by its volume.
Catalyst described in step (8) is water-soluble carbodiimide and DMAP.
Described water-soluble carbodiimide is preferably EDC, and (1-(3-dimethylamino-propyl)-3-ethyl carbon two is sub-
Amine hydrochlorate).
The tertiary amine groups polysiloxanes with Amino End Group described in step (8) and the described poly-silica of single-ended carboxylic acid
Alkane 1:(2.2 in molar ratio～2.4) proportioning.
The described tertiary amine groups polysiloxanes with Amino End Group, single-ended carboxylic acid polysiloxanes, water-soluble carbon
It is 1:2.2～2.4:1.4:0.5 proportioning in molar ratio that diimine and DMAP are preferably.
Organic solvent E described in step (8) is preferably dichloromethane.
The quality consumption of the organic solvent E described in step (8) be preferably single-ended carboxyl polysiloxanes+with
2 times of the tertiary amine groups polysiloxanes gross mass of Amino End Group.
The condition of the reaction described in step (8) is preferably reacts 20～24h in 25～30 DEG C.
Specifically comprising the following steps that of purification described in step (8) is washed with deionized product, takes organic facies
Decompression distillation, obtains tertiary amine groups polysiloxane block copolymers after purification
(PDMS-b-(PDMS-g-DMAA)-b-PDMS), wherein remains the single-ended silicone oil of carboxyl of excess at next
Step removes.
The number of times of described washing is preferably 3～5 times.
Halogenated hydrocarbons described in step (9) is preferably in benzyl chloride, bromination of n-butane and 1-bromo normal hexane
At least one.
Tertiary amine groups polysiloxane block copolymers described in step (9) is gathered by tertiary amine groups with described halogenated hydrocarbons
Tertiary amine group and halogenated hydrocarbons mol ratio 1:(3～5 in silicone block copolymer) proportioning.
Organic solvent F described in step (9) be preferably in dehydrated alcohol and methanol one or both, excellent
Elect dehydrated alcohol as.
The Functionality, quality and appealing design of the organic solvent F described in step (9) is elected as and is equivalent to tertiary amine groups polysiloxane block altogether
Polymers+halogenated hydrocarbons gross mass.
The condition of the reaction described in step (9) is preferably reacts 24～30h in 85～95 DEG C.
Purification described in step (9) specifically comprise the following steps that decompression distillation, the crude product obtained uses water again
Dissolve, add in petroleum ether and extract, discard containing halogenated hydrocarbons and the petroleum ether layer that remains single-ended silicone oil of carboxyl,
Remaining aqueous solution rotation is vacuum dried 24～30h after steaming at 90～100 DEG C, obtains the poly-silicon containing quaternary ammonium salt group
Oxygen alkane block copolymer (PDMS-b-(PDMS-g-QAS)-b-PDMS).
By D in rate-determining steps (2)4 HAnd D4Rate of charge, PA-PDMS-co-PHMS-PA can be adjusted
In chain length and graft ratio；By D in rate-determining steps (5)3With the rate of charge of n-BuLi, permissible
Adjust the length of two ends PDMS block；By changing the kind of halogenated hydrocarbons in step (9), thus it is possible to vary season
The kind of ammonium salt groups；By above-mentioned 3 kinds of adjustment, can prepare different block length, different graft ratio with
And the product of difference quaternary ammonium salt group type.
The present invention has such advantages as relative to prior art and effect:
(1) quaternary ammonium salt have uniqueness surface activity, and penetration by force, relatively easily biological-degradable, has a broad antifungal spectrum.
It is generally acknowledged that quaternary ammonium salt is that it can suppress the sprouting of mycelial growth and spore, simultaneously to the Antibacterial Mechanism of fungus
Also can destroy the integrity of cell membrane.Polymeric quaternary ammonium salt groups has good inhibitory action to antibacterial, and
Compared to inorganic antiseptic and natural antibacterial agent, also have that chemical stability is good, residual toxicity is low, antibacterial effect
The advantage such as the most lasting.
(2) PDMS-b-(PDMS-g-QAS)-b-PDMS is soluble in water, it is not necessary to the auxiliary agents such as emulsifying agent
It is configured to the aqueous solution of variable concentrations, convenient use.It addition, compare and PDMS-g-QAS, blocked it
After PDMS-b-(PDMS-g-QAS)-b-PDMS become typical amphiphilic macromolecular, it is possible to good viscous
It is attached to the surface of lyophobic dust so that it is the growth of banana blight bacteria can be suppressed the most in the solution,
And on hydrophobic Leaf of banana surface, fungus can be infected and effectively prevent and treat.
Accompanying drawing explanation
Fig. 1 is the structure chart of PDMS-b-(PDMS-g-QAS)-b-PDMS；Wherein, R be PDMS-g-BC,
PDMS-g-BB and PDMS-g-HEB, represents in the grafting segment of centre respectively, with PDMS as main chain,
Containing zephiran, alkyl dimethyl butyl ammonium chloride and alkyl dimethyl hexyl ammonium chloride
The polysiloxane-grafted quaternary ammonium salt of side base.
Fig. 2 is the Infrared Characterization spectrogram of PDMS-b-(PDMS-g-BC)-b-PDMS.
Fig. 3 is the sign spectrogram of PDMS-b-(PDMS-g-BC)-b-PDMS nucleus magnetic hydrogen spectrum and corresponding chemical potential
The schematic diagram moved.
Fig. 4 is banana blight bacteria mycelia block PDMS-b-(the PDMS-g-QAS)-b-PDMS at different structure
PDA culture medium in cultivate after 5 days, the graph of a relation between the concentration of the suppression ratio medicament of mycelial growth.
Fig. 5 is that banana blight bacteria mycelia block is at different percent graftings
After the PDA culture medium of PDMS-b-(PDMS-g-BC)-b-PDMS is cultivated 5 days, the suppression of mycelial growth
Graph of a relation between the concentration of rate medicament.
Fig. 6 is to characterize it by the way of contact angle hydrophobic containing block quaternary ammonium salt and without block quaternary ammonium salt
The result of the adhesive attraction on property surface.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention
It is not limited to this.
Agents useful for same of the present invention is all commercially available.
The preparation of embodiment 1 block macromole quaternary ammonium salt, structure is as shown in Figure 1
One, the preparation of PDMS-b-(PDMS-g-BC)-b-PDMS:
(1) protection of amino disiloxane end socket (BAPTMDS): be furnished with mechanical agitation, condensing tube
In reactor, by material molar ratio BAPTMDS: phthalic anhydride=1:2.2 feeds intake, and uses raw material
The oxolane that gross mass is 2 times dissolves raw material, reacts 4 hours at 60 DEG C.After reaction terminates, decompression distillation removes
Remove solvent THF, use chloroform lysate, with 55 DEG C of hot wash products 5 times, take chloroform layer decompression distillation,
The end socket BAPTMDS-PA that must be protected by phthalic anhydride2。
(2) synthesis of hydrogen containing siloxane (PA-PDMS-co-PHMS-PA): under the conditions of 25 DEG C, to joining
Have in the reactor of mechanical stirring device, condensing tube, be D by raw material molar ratio4 H: D4: end socket=4.43:
13.29:1 feeds intake, and dissolves raw material with the chloroform with the quality such as raw material, and being subsequently added concentration is 80wt%'s
Sulfuric acid solution, the consumption of sulfuric acid solution is D4 H+D4The 2% of quality, starts stirring, reacts 12 little under room temperature
Stop time after.After reaction terminates, use sodium bicarbonate aqueous solution neutralisation of sulphuric acid, take chloroform layer 150 DEG C after standing and subtract
Pressure distillation 4 hours, obtains hydrogen containing siloxane PA-PDMS-co-PHMS-PA.
(3) tertiary amine groups polysiloxanes (PA2-PDMS-g-DMAA) synthesis: be furnished with mechanical agitation, cold
In the reactor of solidifying pipe, nitrogen breather and Dropping funnel, add the DMAA of metering, open stirring, rise
Temperature also starts to be passed through nitrogen, adds Karstedt ' s catalyst afterwards, by every gram of hydrogen containing siloxane correspondence about 5
Karstedt ' the s catalyst of microgram adds；After 15min, temperature rises to 80 DEG C, then begins to drip hydrogeneous poly-silicon
Oxygen alkane PA-PDMS-co-PHMS-PA, makes rubbing of silicon hydrogen and DMAA in PA-PDMS-co-PHMS-PA
Your ratio is 1:2, stops after reacting 48 hours.After reaction terminates, decompression is distilled off the DMAA of excess,
Obtain PA2-PDMS-g-DMAA。
(4) tertiary amine groups the polysiloxanes ((NH of Amino End Group2)2-PDMS-g-DMAA) synthesis: be furnished with
Mechanical agitation, condensing tube reactor in, be PA by raw material molar ratio2-PDMS-g-DMAA:N2H4
·H2O=1:4.5 feeds intake, and uses PA2The ethanol that-PDMS-g-DMAA quality is 2 times dissolves raw material, starts and stirs
Mix, react 10 hours at 75 DEG C.After reaction terminates, decompression is distilled off ethanol, water and a hydrazine hydrate, uses
Chloroform lysate, 55 DEG C of water wash 3 times, take chloroform layer decompression distillation, obtain (NH2)2-PDMS-g-DMAA。
(5) synthesis of single-ended hydrogen containing siloxane (PDMS-H): be furnished with mechanical agitation, condensing tube, nitrogen
In the reactor of gas breather, it is D by raw material molar ratio3: n-BuLi=4.5:1 feeds intake,
With with D3Etc. quality oxolane dissolve raw material, be passed through nitrogen, 0 DEG C react 20h, be subsequently adding with just
The dimethylchlorosilane of the amount of the materials such as butyl lithium, continues stirring 1 hour.After reaction terminates, sucking filtration, decompression
Oxolane is distilled off, obtains PDMS-H.
(6) synthesis of single-ended ester polysiloxanes (PDMS-tBMA): be furnished with mechanical agitation, condensing tube,
In the reactor of nitrogen breather and Dropping funnel, add the PDMS-H of metering, open stirring, heat up also
Start logical nitrogen, add chloroplatinic acid catalyst afterwards, by the chlorine platinum of corresponding about 5 micrograms of every gram of hydrogen containing siloxane
Acid adds；After about 10min, temperature rises to 75 DEG C, then begins to drip tBMA, is tBMA and PDMS-H
Mol ratio be 1.2:1, react 12 hours.After reaction terminates, sucking filtration removes the autopolymer of tBMA, subtracts
Pressure is distilled off the tBMA of excess, obtains PDMS-tBMA.
(7) synthesis of single-ended carboxylic acid polysiloxanes (PDMS-COOH): be furnished with mechanical agitation, condensing tube
Reactor in, put into metering PDMS-tBMA, subsequently put into PDMS-tBMA mass 0.8% dense sulfur
Acid (98% sulphuric acid), reacts 3h at 80 DEG C.After reaction terminates, use chloroform lysate, then with isopyknic
Deionized water wash less than 8 to water layer pH, takes chloroform layer decompression distillation, obtains PDMS-COOH.
(8) tertiary amine groups polysiloxane block copolymers (PDMS-b-(PDMS-g-DMAA)-b-PDMS)
Synthesis: in the reactor being furnished with mechanical agitation, condensing tube, by raw material molar ratio be
(NH2)2-PDMS-g-DMAA:PDMS-COOH:EDC:DMAP=1:2.2:1.4:0.5 throws
Material, dissolves raw material with the dichloromethane of raw materials quality 2 times, reacts 20h at 25 DEG C.After reaction terminates, spend
Ionized water washs 3 times, takes organic facies decompression distillation, obtains PDMS-b-(PDMS-g-DMAA)-b-PDMS,
The single-ended silicone oil of carboxyl wherein remaining excess removes in next step.
(9) containing the polysiloxane block copolymers of grafting benzyl chloride group
The synthesis of (PDMS-b-(PDMS-g-BC)-b-PDMS): be furnished with mechanical agitation, condensing tube, nitrogen lead to
In the reactor of device of air and Dropping funnel, add PDMS-b-(the PDMS-g-DMAA)-b-PDMS of metering,
With etc. the ethanol of quality dissolve, open stirring, heat up and start logical nitrogen, the ethanol dissolving chlorination of the quality such as use
Benzyl, making the ratio of tertiary amine group and benzyl chloride in DMAA is 1:3, is slowly added dropwise chlorine at 90 DEG C
Change the ethanol solution of benzyl, after dropping, react 24h at 85 DEG C.After reaction terminates, decompression distillation, obtain
Crude product again with water dissolution, add and petroleum ether extract several times, discard containing halogenated hydrocarbons and remain single-ended
The petroleum ether layer of silicone oil of carboxyl, remaining aqueous solution rotation is vacuum dried 24h at 90 DEG C after steaming, obtains
PDMS-b-(PDMS-g-BC)-b-PDMS。
The Infrared Characterization result of product is as shown in Figure 2: wherein, and 2850～2970cm-1It is-CH3With-CH2-
Stretching vibration absworption peak, 2908cm-1It is N-CH2Stretching vibration absworption peak, 1261cm-1It is Si-CH3's
Deformation vibration absworption peak, 1091cm-1It is the stretching vibration absworption peak of Si-O-Si, 1651cm-1Place is amido link
The stretching vibration absworption peak of middle C=O.700cm simultaneously-1Phenyl ring hydrocarbon out-of-plane bending vibration peak, place and 3030cm-1
Place's hydrocarbon stretching vibration peak of phenyl ring shows the existence of benzene radicals.
The nuclear-magnetism characterization result of product is as shown in Figure 3: product heavy water dissolves, and carries out the sign of nucleus magnetic hydrogen spectrum,
The schematic diagram of result and corresponding chemical displacement is as shown in the figure.
Two, the preparation of PDMS-b-(PDMS-g-BB)-b-PDMS:
(1) protection of amino disiloxane end socket (BAPTMDS): be furnished with mechanical agitation, condensing tube
In reactor, by material molar ratio BAPTMDS: phthalic anhydride=1:2.4 feeds intake, and uses raw material
The dichloromethane that gross mass is 2 times dissolves raw material, reacts 5 hours at 70 DEG C.After reaction terminates, decompression distillation removes
Remove solvent THF, use chloroform lysate, with 60 DEG C of hot wash products 3 times, take chloroform layer decompression distillation,
The end socket BAPTMDS-PA that must be protected by phthalic anhydride2。
(2) synthesis of hydrogen containing siloxane (PA-PDMS-co-PHMS-PA): under room temperature condition, to joining
Have in the reactor of mechanical stirring device, condensing tube, be D by raw material molar ratio4 H: D4: end socket=4.43:
13.29:1 feeds intake, and dissolves raw material with the toluene with the quality such as raw material, and being subsequently added concentration is 85wt%'s
Sulfuric acid solution, the consumption of sulfuric acid solution is D4 H: D4The 3% of quality, starts stirring, reacts 13 little under room temperature
Stop time after.After reaction terminates, use sodium bicarbonate aqueous solution neutralisation of sulphuric acid, take chloroform layer 150 DEG C after standing and subtract
Pressure distillation 4 hours, obtains hydrogen containing siloxane PA-PDMS-co-PHMS-PA.
(3) tertiary amine groups polysiloxanes (PA2-PDMS-g-DMAA) synthesis: be furnished with mechanical agitation, cold
In the reactor of solidifying pipe, nitrogen breather and Dropping funnel, add the DMAA of metering, open stirring, rise
Temperature also starts to be passed through nitrogen, adds Karstedt ' s catalyst afterwards, by every gram of hydrogen containing siloxane correspondence about
Karstedt ' the s catalyst of 7.5 micrograms adds；After 15min, temperature rises to 90 DEG C, then begins to drip hydrogeneous
Polysiloxanes PA-PDMS-co-PHMS-PA, makes silicon hydrogen and DMAA in PA-PDMS-co-PHMS-PA
Mol ratio be 1:3, after reacting 60 hours stop.After reaction terminates, decompression is distilled off the DMAA of excess,
Obtain PA2-PDMS-g-DMAA。
(4) tertiary amine groups the polysiloxanes ((NH of Amino End Group2)2-PDMS-g-DMAA) synthesis: be furnished with
Mechanical agitation, condensing tube reactor in, be PA by raw material molar ratio2-PDMS-g-DMAA:N2H4
·H2O=1:5 feeds intake, and uses PA2The methanol that-PDMS-g-DMAA quality is 2 times dissolves raw material, starts and stirs
Mix, react 12 hours at 80 DEG C.After reaction terminates, decompression is distilled off ethanol, water and a hydrazine hydrate, uses
Chloroform lysate, 60 DEG C of water wash 5 times, take chloroform layer decompression distillation, obtain (NH2)2-PDMS-g-DMAA。
(5) synthesis of single-ended hydrogen containing siloxane (PDMS-H): be furnished with mechanical agitation, condensing tube, nitrogen
In the reactor of gas breather, it is D by raw material molar ratio3: n-BuLi=4.5:1 feeds intake,
With with D3Etc. quality chloroform dissolve raw material, be passed through nitrogen, 5 DEG C react 22h, be subsequently adding with just
The dimethylchlorosilane of the amount of the materials such as butyl lithium, continues stirring 2 hours.After reaction terminates, sucking filtration, decompression
Oxolane is distilled off, obtains PDMS-H.
(6) synthesis of single-ended ester polysiloxanes (PDMS-tBMA): be furnished with mechanical agitation, condensing tube,
In the reactor of nitrogen breather and Dropping funnel, add the PDMS-H of metering, open stirring, heat up also
Start logical nitrogen, add chloroplatinic acid catalyst afterwards, by the chlorine of corresponding about 7.5 micrograms of every gram of hydrogen containing siloxane
Platinic acid adds；After about 10min, temperature rises to 80 DEG C, then begins to drip tBMA, is tBMA and PDMS-H
Mol ratio be 1.3:1, react 13 hours.After reaction terminates, sucking filtration removes the autopolymer of tBMA, subtracts
Pressure is distilled off the tBMA of excess, obtains PDMS-tBMA.
(7) synthesis of single-ended carboxylic acid polysiloxanes (PDMS-COOH): be furnished with mechanical agitation, condensing tube
Reactor in, put into metering PDMS-tBMA, subsequently put into PDMS-tBMA mass 0.9% dense sulfur
Acid, reacts 4h at 85 DEG C.After reaction terminates, use chloroform lysate, then wash with isopyknic deionization
Wash to water layer pH less than 8, take chloroform layer decompression distillation, obtain PDMS-COOH.
(8) tertiary amine groups polysiloxane block copolymers (PDMS-b-(PDMS-g-DMAA)-b-PDMS)
Synthesis: in the reactor being furnished with mechanical agitation, condensing tube, by raw material molar ratio be
(NH2)2-PDMS-g-DMAA:PDMS-COOH:EDC:DMAP=1:2.3:1.4:0.5 throws
Material, dissolves raw material with the dichloromethane of raw materials quality 2 times, reacts 22h at 28 DEG C.After reaction terminates, spend
Ionized water washs 5 times, takes organic facies decompression distillation, obtains PDMS-b-(PDMS-g-DMAA)-b-PDMS,
The single-ended silicone oil of carboxyl wherein remaining excess removes in next step.
(9) containing the polysiloxane block copolymers of grafting Butyldimethyl ammonium chloride group
The synthesis of (PDMS-b-(PDMS-g-BB)-b-PDMS): be furnished with mechanical agitation, condensing tube, nitrogen lead to
In the reactor of device of air and Dropping funnel, add PDMS-b-(the PDMS-g-DMAA)-b-PDMS of metering,
With etc. the methanol of quality dissolve, open stirring, heat up and start logical nitrogen, just dissolving bromo with the methanol of quality
Butane, making the ratio of tertiary amine group and bromination of n-butane in DMAA is 1:4, at 90 DEG C slowly
The methanol solution of dropping bromination of n-butane, after dropping, reacts 27h at 90 DEG C.After reaction terminates, decompression
Distillation, the crude product obtained, again with water dissolution, adds and extracts several times in petroleum ether, discard containing halogenated hydrocarbons and
Remaining the petroleum ether layer of single-ended silicone oil of carboxyl, remaining aqueous solution rotation is vacuum dried 27h after steaming at 90 DEG C,
To PDMS-b-(PDMS-g-BB)-b-PDMS.
Three, the preparation of PDMS-b-(PDMS-g-HEB)-b-PDMS:
(1) protection of amino disiloxane end socket (BAPTMDS): be furnished with mechanical agitation, condensing tube
In reactor, by material molar ratio BAPTMDS: phthalic anhydride=1:2.6 feeds intake, and uses raw material
The oxolane that gross mass is 2 times dissolves raw material, reacts 6 hours at 80 DEG C.After reaction terminates, decompression distillation removes
Remove solvent THF, use chloroform lysate, with 65 DEG C of hot wash products 4 times, take chloroform layer decompression distillation,
The end socket BAPTMDS-PA that must be protected by phthalic anhydride2。
(2) synthesis of hydrogen containing siloxane (PA-PDMS-co-PHMS-PA): under room temperature condition, to joining
Have in the reactor of mechanical stirring device, condensing tube, be D by raw material molar ratio4 H: D4: end socket=4.43:
13.29:1 feeds intake, and dissolves raw material with the chloroform with the quality such as raw material, and being subsequently added concentration is 86wt%'s
Sulfuric acid solution, the consumption of sulfuric acid solution is D4 H: D4The 3% of quality, starts stirring, reacts 14 little under room temperature
Stop time after.After reaction terminates, use sodium bicarbonate aqueous solution neutralisation of sulphuric acid, take chloroform layer 150 DEG C after standing and subtract
Pressure distillation 4 hours, obtains hydrogen containing siloxane PA-PDMS-co-PHMS-PA.
(3) tertiary amine groups polysiloxanes (PA2-PDMS-g-DMAA) synthesis: be furnished with mechanical agitation, cold
In the reactor of solidifying pipe, nitrogen breather and Dropping funnel, add the DMAA of metering, open stirring, rise
Temperature also starts to be passed through nitrogen, adds Karstedt ' s catalyst afterwards, by every gram of hydrogen containing siloxane correspondence about
Karstedt ' the s catalyst of 10 micrograms adds；After 15min, temperature rises to 100 DEG C, then begins to drip hydrogeneous
Polysiloxanes PA-PDMS-co-PHMS-PA, makes silicon hydrogen and DMAA in PA-PDMS-co-PHMS-PA
Mol ratio be 1:4, after reacting 72 hours stop.After reaction terminates, decompression is distilled off the DMAA of excess,
Obtain PA2-PDMS-g-DMAA。
(4) tertiary amine groups the polysiloxanes ((NH of Amino End Group2)2-PDMS-g-DMAA) synthesis: be furnished with
Mechanical agitation, condensing tube reactor in, be PA by raw material molar ratio2-PDMS-g-DMAA:N2H4
·H2O=1:5.5 feeds intake, and uses PA2The ethanol that-PDMS-g-DMAA quality is 2 times dissolves raw material, starts and stirs
Mix, react 14 hours at 85 DEG C.After reaction terminates, decompression is distilled off ethanol, water and a hydrazine hydrate, uses
Chloroform lysate, 65 DEG C of water wash 4 times, take chloroform layer decompression distillation, obtain (NH2)2-PDMS-g-DMAA。
(5) synthesis of single-ended hydrogen containing siloxane (PDMS-H): be furnished with mechanical agitation, condensing tube, nitrogen
In the reactor of gas breather, it is D by raw material molar ratio3: n-BuLi=4.5:1 feeds intake,
With with D3Etc. quality oxolane dissolve raw material, be passed through nitrogen, 10 DEG C react 24h, be subsequently adding with just
The dimethylchlorosilane of the amount of the materials such as butyl lithium, continues stirring 1 hour.After reaction terminates, sucking filtration, decompression
Oxolane is distilled off, obtains PDMS-H.
(6) synthesis of single-ended ester polysiloxanes (PDMS-tBMA): be furnished with mechanical agitation, condensing tube,
In the reactor of nitrogen breather and Dropping funnel, add the PDMS-H of metering, open stirring, heat up also
Start logical nitrogen, add chloroplatinic acid catalyst afterwards, by the chlorine of corresponding about 10 micrograms of every gram of hydrogen containing siloxane
Platinic acid adds；After about 10min, temperature rises to 80 DEG C, then begins to drip tBMA, is tBMA and PDMS-H
Mol ratio be 1.4:1, react 14 hours.After reaction terminates, sucking filtration removes the autopolymer of tBMA, subtracts
Pressure is distilled off the tBMA of excess, obtains PDMS-tBMA.
(7) synthesis of single-ended carboxylic acid polysiloxanes (PDMS-COOH): be furnished with mechanical agitation, condensing tube
Reactor in, put into metering PDMS-tBMA, subsequently put into PDMS-tBMA mass 1% dense sulfur
Acid, reacts 4h at 90 DEG C.After reaction terminates, use chloroform lysate, then wash with isopyknic deionization
Wash to water layer pH less than 8, take chloroform layer decompression distillation, obtain PDMS-COOH.
(8) tertiary amine groups polysiloxane block copolymers (PDMS-b-(PDMS-g-DMAA)-b-PDMS)
Synthesis: in the reactor being furnished with mechanical agitation, condensing tube, by raw material molar ratio be
(NH2)2-PDMS-g-DMAA:PDMS-COOH:EDC:DMAP=1:2.4:1.4:0.5 throws
Material, dissolves raw material with the dichloromethane of raw materials quality 2 times, reacts 24h at 30 DEG C.After reaction terminates, spend
Ionized water washs 4 times, takes organic facies decompression distillation, obtains PDMS-b-(PDMS-g-DMAA)-b-PDMS,
The single-ended silicone oil of carboxyl wherein remaining excess removes in next step.
(9) containing the polysiloxane block copolymers of grafting hexyl ditallowdimethyl ammonium bromide group
The synthesis of (PDMS-b-(PDMS-g-HEB)-b-PDMS): be furnished with mechanical agitation, condensing tube, nitrogen lead to
In the reactor of device of air and Dropping funnel, add PDMS-b-(the PDMS-g-DMAA)-b-PDMS of metering,
With etc. the ethanol of quality dissolve, open stirring, heat up and start logical nitrogen, the ethanol dissolving 1-bromine of the quality such as use
For normal hexane, making the ratio of tertiary amine group and 1-bromo normal hexane in DMAA is 1:5, at 100 DEG C
Under be slowly added dropwise the ethanol solution of bromo normal hexane, after dropping, react 30h at 95 DEG C.After reaction terminates,
Decompression distillation, the crude product obtained with water dissolution, adds and extracts several times in petroleum ether, discard containing halogenated hydrocarbons again
And remaining the petroleum ether layer of single-ended silicone oil of carboxyl, remaining aqueous solution rotation is vacuum dried after steaming at 100 DEG C
30h, obtains PDMS-b-(PDMS-g-HEB)-b-PDMS.
The method of embodiment 2 block macromole quaternary ammonium salt suppression banana blight bacteria mycelial growth:
One, the detection process of PDMS-b-(PDMS-g-BC)-b-PDMS suppression banana blight bacteria mycelial growth
(1) preparation of block macromole quaternary ammonium salt solution: containing of metering is grafted benzyl chloride base
Polysiloxane block copolymers PDMS-b-(the PDMS-g-BC)-b-PDMS of group is dissolved in sterilized water, is configured to
0 (being used for compareing), 0.25g/L, 0.5g/L, 0.75g/L, 1.0g/L, 1.25g/L, 1.5g/L.Its
The number-average molecular weight of middle grafting segment segment PDMS-g-BC is 5.0 × 103, length ratio is PDMS:
PDMS-g-BC:PDMS=1:5:1, in the block (PDMS-g-BC) containing quaternary ammonium salt group, its grafting
Shared by the chain link of quaternary ammonium salt group, total chain number ratio (graft ratio) is 1/4.
(2) preparation of culture plate: by the block macromole quaternary ammonium salt solution of each concentration prepared and Ma Ling
Potato glucose agar medium (PDA, wherein, Rhizoma Solani tuber osi: glucose: the agar proportioning of 10:1:1 in mass ratio)
Mixing, and make culture plate by the mode being down flat plate.
(3) measuring and calculating of mycelial growth inhibition rate: beat with card punch and take banana blight bacteria (Agricultural University Of South China
Resource environment institute Plant Pathology system fungal studies room give, and can manage in China General Microbiological culture presevation
Center or other microbial preservation companies are commercially available) for trying the mycelia block (a diameter of 6mm) of colony edge,
Bacterium faces down, and moves to flat board central authorities, after being placed in 28 DEG C of constant incubators training 5 days, surveys by decussation method
Amount colony diameter, and calculate mycelial growth inhibition rate according to following formula (1) and formula (2).
Bacterium colony extension diameter (mm)=bacterium colony average diameter (mm)-6mm (1)
Suppression ratio=(comparison bacterium colony extension diameter-process bacterium colony extension diameter)/comparison bacterium colony extension diameter (2)
Two, the detection process of PDMS-b-(PDMS-g-BB)-b-PDMS suppression banana blight bacteria mycelial growth
Except block macromole quaternary ammonium salt used in step (1) is PDMS-b-(PDMS-g-BB)-b-PDMS,
I.e. outside the polysiloxane block copolymers containing grafting normal-butyl bromination ammonium group, remaining is all identical with step one.
Three, the detection of PDMS-b-(PDMS-g-HEB)-b-PDMS suppression banana blight bacteria mycelial growth
Journey
Except block macromole quaternary ammonium salt used in step (1) is PDMS-b-(PDMS-g-HEB)-b-PDMS,
I.e. outside the polysiloxane block copolymers containing grafting n-hexyl ammonium bromide group, remaining is all identical with step one.
Four, testing result
Identical number-average molecular weight, identical graft ratio, PDMS-b-(the PDMS-g-QAS)-b-PDMS of different structure
(embodiment 1) is to the relation such as Fig. 4 institute between growth inhibition ratio and the drug level of banana blight bacteria mycelia
Show.Result shows, the effect of PDMS-b-(PDMS-g-BC)-b-PDMS suppression mycelial growth is best and dense
When degree reaches 1.5g/L, banana blight bacteria mycelia is almost complete absence of growth；Other two kinds of structures
PDMS-b-(PDMS-g-QAS)-b-PDMS, also the growth to mycelia also has good inhibiting effect.
Embodiment 3:
(1) PDMS-b-(the PDMS-g-BC)-b-PDMS of the different graft ratio of preparation, preparation method and embodiment
1 step one is essentially identical, and difference is: graft ratio is 1/3 (D4 H: D4: end socket=6:12:1), 1/4
(D4 H: D4: end socket=4.43:13.29:1), 1/5 (D4 H: D4: BAPTMDS-PA2=3.51:14.04:
1)、1/6(D4 H: D4: end socket=2.91:14.53:1).
PDMS-b-(PDMS-g-BC)-b-PDMS is at identical number-average molecular weight, identical structure, different graft ratio
In the case of, to the relation between growth inhibition ratio and the drug level of banana blight bacteria mycelia as shown in Figure 5.
Result shows, along with the rising of quaternary ammonium salt group percent grafting, the inhibitory action to banana blight bacteria mycelial growth
Strengthen, but when solution concentration is higher, this reinforced effects is the most notable.
Embodiment 4:
Preparing three kinds of graft ratios is 1/4, and number-average molecular weight is 5000, without the PDMS-g-QAS of block
(PDMS-g-BC, PDMS-g-BB, PDMS-g-HEB), concrete preparation method is as follows: by embodiment 1
In the product for preparing in step (3) in one to three quaternized, will PA2-PDMS-g-DMAA presses one
In three prepared by step (9), obtains PDMS-g-QAS (non-block quaternary ammonium salt), wherein, D4 H: D4:
End socket=4.43:13.29:1；It is configured to the solution of 1g/L with deionized water, obtains the quaternary ammonium salt without block
Solution a.Product and small molecule quaternary ammonium salt benzalkonium chloride in Example 1 are configured to 1 with deionized water respectively
The solution of g/L, obtains the solution b containing block quaternary ammonium salt and small molecule quaternary ammonium saline solution c.
Hydrophobic microscope slide is immersed in respectively in tri-kinds of solution of above-mentioned a, b, c and deionized water.After 1 hour,
Take out natural air drying, soak respectively 1 hour in deionized water, repeat this step 2 time.To above-mentioned 4 kinds of differences
Microscope slide after process carries out the test of contact angle, and result is as shown in Figure 6.Visible embodiment 1 prepares
Block polysiloxane grafting quaternary ammonium salt than non-block polysiloxane grafting quaternary ammonium salt can preferably stick to hydrophobic
The surface of property.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned enforcement
The restriction of example, the change made, modifies, replaces under other any spirit without departing from the present invention and principle
In generation, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. block macromole quaternary ammonium salt purposes in suppression banana blight bacteria growing, it is characterised in that: institute
The structural formula of the block macromole quaternary ammonium salt stated is as shown in formula A:
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 1
On the way, it is characterised in that: described R is
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 1
On the way, it is characterised in that: the value of described m is 4～16；The value of described n is 8～48；M, n are
The multiple of 4.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 1
On the way, it is characterised in that: the number-average molecular weight of the described polysiloxane backbone in block macromole quaternary ammonium salt is
2×103～1 × 104；
The chain number being grafted quaternary ammonium salt group in described block macromole quaternary ammonium salt accounts for the grafting total chain number of segment
1/3～1/8.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 1
On the way, it is characterised in that: described block macromole quaternary ammonium salt is made by the steps and obtains:
(1) protection of primary amino radical in double (3-the aminopropyl)-1,1,3,3-tetramethyl disiloxane of 1,3-: toward organic
Solvent orange 2 A adds phthalic anhydride and 1, double (the 3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane, instead
Should；The product purification obtaining reaction, obtains BAPTMDS-PA2；
(2) synthesis of hydrogen containing siloxane: with BAPTMDS-PA2, octamethylcy-clotetrasiloxane and tetramethyl
Basic ring tetrasiloxane is raw material, with sulfuric acid solution as catalyst, reacts in organic solvent B；To reacting
The product purification arrived, obtains hydrogen containing siloxane；
(3) synthesis of tertiary amine groups polysiloxanes: under an inert atmosphere, toward containing that step (2) prepares
Hydrogen polysiloxanes adds DMAA, reacts under catalyst action；The product that reaction is obtained
Purification, obtains tertiary amine groups polysiloxanes；
(4) deprotection of the Amino End Group of tertiary amine groups polysiloxanes: add step (3) in organic solvent C
The tertiary amine groups polysiloxanes prepared and a hydrazine hydrate, reaction；The product purification obtaining reaction, obtains
Slough the tertiary amine groups polysiloxanes with Amino End Group of phthalic anhydride protection；
(5) synthesis of single-ended hydrogen containing siloxane: under an inert atmosphere, adds pregnancy in organic solvent D
Basic ring trisiloxanes and n-butyllithium solution, reaction；It is subsequently added into dimethylchlorosilane and terminates reaction, to instead
The product purification that should obtain, obtains single-ended hydrogen containing siloxane；
(6) synthesis of single-ended ester group polysiloxanes: under an inert atmosphere, prepared by past step (5) single-ended
Hydrogen containing siloxane adds Tert-butyl Methacrylate, reacts under catalyst action；Reaction is obtained
Product purification, obtains single-ended ester group polysiloxanes；
(7) synthesis of single-ended carboxyl polysiloxanes: in single-ended ester group polysiloxanes prepared by step (5)
Add concentrated sulphuric acid, reaction；The product purification obtaining reaction, obtains single-ended carboxyl polysiloxanes；
(8) synthesis of polysiloxane block copolymers: add prepared by step (5) in organic solvent E
The tertiary amine groups polysiloxanes with Amino End Group that single-ended carboxyl polysiloxanes and step (4) prepare, is urging
React under agent effect；The product purification obtaining reaction, obtains tertiary amine groups polysiloxane block copolymers；
(9) synthesis of the polysiloxane block copolymers containing quaternary ammonium salt group: under an inert atmosphere, toward organic
Solvent F adds tertiary amine groups polysiloxane block copolymers and halogenated hydrocarbons, reaction；The product that reaction is obtained
Purification, obtains the polysiloxane block copolymers containing quaternary ammonium salt group.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 5
On the way, it is characterised in that:
Double (3-the aminopropyl)-1,1,3,3-tetramethyl disiloxane of 1,3-described in step (1) is with described
Phthalic anhydride 1:(2.2 in molar ratio～2.6) proportioning；
Tetramethyl-ring tetrasiloxane described in step (2), described octamethylcy-clotetrasiloxane are with described
BAPTMDS-PA22.81～6:11.24～13.29:1 proportioning in molar ratio；
Hydrogen containing siloxane described in step (3) and described DMAA press hydrogen containing siloxane
Middle hydrogen group and DMAA mol ratio are 1:(2～4) proportioning；
Tertiary amine groups polysiloxanes described in step (4) and described hydrazine hydrate 1:(4.5 in molar ratio～
5.5) proportioning；
N-BuLi, hexamethyl cyclotrisiloxane and dimethylchlorosilane described in step (5) are in molar ratio
For 1:(4.5～22.5): 1 proportioning；
Single-ended hydrogen containing siloxane described in step (6) is with described Tert-butyl Methacrylate in molar ratio
For 1:(1.2～1.4) proportioning；
The quality consumption of the concentrated sulphuric acid described in step (7) is described single-ended ester group polysiloxanes quality
0.8～1%；
The tertiary amine groups polysiloxanes with Amino End Group described in step (8) and the described poly-silica of single-ended carboxylic acid
Alkane 1:(2.2 in molar ratio～2.4) proportioning；
Tertiary amine groups polysiloxane block copolymers described in step (9) is gathered by tertiary amine groups with described halogenated hydrocarbons
Tertiary amine group and halogenated hydrocarbons mol ratio 1:(3～5 in silicone block copolymer) proportioning.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 5
On the way, it is characterised in that:
The condition of the reaction described in step (1) is to react 4～6h in 60～80 DEG C；
Reaction described in step (2) is to react 12～14h at 25～30 DEG C；
The condition of the reaction described in step (3) is to react 48～72h in 80～100 DEG C；
The condition of the reaction described in step (4) is to react 10～14h in 75～85 DEG C；
The condition of the reaction described in step (5) is to react 20～24h in 0～10 DEG C；
The condition terminating reaction described in step (5) is in 0～10 DEG C of stirring reaction 1～2h；
The condition of the reaction described in step (6) is to react 12～14h in 75～85 DEG C；
The condition of the reaction described in step (7) is to react 3～4h in 80～90 DEG C；
The condition of the reaction described in step (8) is to react 20～24h in 25～30 DEG C；
The condition of the reaction described in step (9) is to react 24～30h in 85～95 DEG C.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 5
On the way, it is characterised in that:
Sulfuric acid solution described in step (2) be concentration be the sulfuric acid solution of 80～90wt%；
The quality consumption of the sulfuric acid solution described in step (2) is equivalent to octamethylcy-clotetrasiloxane+tetramethyl
The 2～4% of ring four silica gross mass；
Catalyst described in step (3) is Karstedt ' s catalyst；
Catalyst described in step (6) is chloroplatinic acid catalyst；
Concentrated sulphuric acid described in step (7) be concentration be the sulphuric acid of 98wt%；
Catalyst described in step (8) is EDC and DMAP；
Halogenated hydrocarbons described in step (9) be in benzyl chloride, bromination of n-butane and 1-bromo normal hexane at least
A kind of.
Block macromole quaternary ammonium salt use in suppression banana blight bacteria growing the most according to claim 1
On the way, it is characterised in that:
Organic solvent A described in step (1) is one or both in oxolane and chloroform；
Organic solvent B described in step (2) is one or both in chloroform and toluene；
Organic solvent C described in step (4) is one or both in dehydrated alcohol and methanol；
Organic solvent D described in step (5) is one or both in oxolane and chloroform；
Organic solvent E described in step (8) is dichloromethane；
Organic solvent F described in step (9) is one or both in dehydrated alcohol and methanol.
The most according to claim 1, block macromole quaternary ammonium salt is in suppression banana blight bacteria growing
Purposes, it is characterised in that:
The step of the purification described in step (1) is as follows: organic solvent A is distilled off by decompression, uses chlorine
Imitative lysate, with 55～65 DEG C of hot wash products, takes chloroform layer decompression distillation, obtains after purification
BAPTMDS-PA2；
The step of the purification described in step (2) is specific as follows: use sodium bicarbonate aqueous solution neutralisation of sulphuric acid, quiet
Postpone and take chloroform layer decompression distillation, obtain hydrogen containing siloxane after purification；
The step of the purification described in step (3) is as follows: decompression is distilled off the DMAA of excess,
Obtain tertiary amine groups polysiloxanes after purification；
The step of the purification described in step (4) is as follows: decompression is distilled off organic solvent C, water and a water
Close hydrazine, use chloroform lysate, 55～65 DEG C of water washings, take chloroform layer decompression distillation, obtain after purification
Tertiary amine groups polysiloxanes with Amino End Group；
Purification described in step (5) specifically comprise the following steps that sucking filtration, decompression distillation, obtain after purification
Single-ended hydrogen containing siloxane；
Purification described in step (6) specifically comprise the following steps that sucking filtration, decompression distillation, obtain after purification
Single-ended ester group polysiloxanes；
Chloroform lysate is used in specifically comprising the following steps that of purification described in step (7), then uses deionized water
Wash to water layer pH less than 8, take chloroform layer decompression distillation, obtain single-ended carboxyl polysiloxanes after purification；
Specifically comprising the following steps that of purification described in step (8) is washed with deionized product, takes organic facies
Decompression distillation, obtains tertiary amine groups polysiloxane block copolymers after purification；
Purification described in step (9) specifically comprise the following steps that decompression distillation, the crude product obtained uses water again
Dissolve, add in petroleum ether and extract, discard containing halogenated hydrocarbons and the petroleum ether layer that remains single-ended silicone oil of carboxyl,
Remaining aqueous solution rotation is vacuum dried 24～30h after steaming at 90～100 DEG C, obtains the poly-silicon containing quaternary ammonium salt group
Oxygen alkane block copolymer.
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| CN201610278195.5A CN105901013B (en) | 2016-04-28 | 2016-04-28 | Block macromolecular quaternary ammonium salt is inhibiting the purposes in banana blight bacteria growth |
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Cited By (3)
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| CN108641087A (en) * | 2018-05-23 | 2018-10-12 | 华南理工大学 | A kind of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes and the preparation method and application thereof |
| CN110724260A (en) * | 2019-10-18 | 2020-01-24 | 华南理工大学 | Super-hydrophilic main chain type quaternary ammonium salt and preparation method and application thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108641087A (en) * | 2018-05-23 | 2018-10-12 | 华南理工大学 | A kind of two block macromolecular quaternary ammonium salts of the segment containing polysiloxanes and the preparation method and application thereof |
| CN110724260A (en) * | 2019-10-18 | 2020-01-24 | 华南理工大学 | Super-hydrophilic main chain type quaternary ammonium salt and preparation method and application thereof |
| CN110724260B (en) * | 2019-10-18 | 2021-12-21 | 华南理工大学 | Super-hydrophilic main chain type quaternary ammonium salt and preparation method and application thereof |
| 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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