CN109593210A - Antifouling antibacterial sand of one kind and preparation method thereof - Google Patents
Antifouling antibacterial sand of one kind and preparation method thereof Download PDFInfo
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- 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
- C08G77/04—Polysiloxanes
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- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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Abstract
The present invention provides a kind of preparation methods of antifouling antibacterial sand, belong to inorganic building material preparation technical field.Sand is sieved, is cleaned by the present invention, obtains the pretreatment grains of sand;The modified grains of sand are obtained by one layer of cationic surfactant of modified cladding first on the pretreatment grains of sand;One layer of silicon oxide layer is connected on the modified grains of sand using polycondensation reaction, obtains the silica grains of sand;The silica grains of sand are acylated, obtain being acylated the grains of sand;The grains of sand and the bis- alkyl of bifunctional group polymer N- are acylated, quaternized-PEI occurs graft reaction, obtains antifouling antibacterial sand.It is of the invention it is antifouling it is antibacterial it is husky successively coat silicon oxide layer and dual functional polymer layer, finally with excellent hydrophobic, anti-pollution and bacteriostasis property.From embodiment as can be seen that antifouling antibacterial husky contact angle >=143 ° provided by the invention, roll angle≤10 °, sterilizing rate is up to 96% or more.
Description
Technical field
The present invention relates to inorganic building material, landscape surfacing preparation technical field, more particularly to one kind are antifouling antibacterial
Sand and preparation method thereof.
Background technique
Harsh Service Environment, makes strand concrete structure significant corrosion problems occur, influences its service life and safety
Property.The safe O&M of strand Important Project can not be ignored, and foundation engineering material and performance boost research urgently carry out.Exploitation,
Using and protection ocean during, concrete works corrosion and biodeterioration be the huge difficult problem that can not avoid always.How
The erosion for controlling chloride ion becomes a very important project for improving armored concrete durability.To prevent chloride permeability
Erosion to reinforced concrete structure, the main method taken at present prepare high performance concrete, using epoxy-coated reinforcement,
Apply impressed current cathodic protection, coating protection etc. is carried out to concrete surface.Wherein concrete surface protective coating is to structure
Surfacecti proteon is carried out, can effectively prevent moisture and eater enters inside, extend the service life of system, is to improve concrete knot
The important means of structure durability.This method has many advantages, such as that economical, beautiful, efficient, construction is convenient simultaneously.
Polymer matrix coating is high, soft using there are film brittleness caused by some problems, such as crosslink density height at present
Poor toughness (poor fluidity in repairing concrete crack), impact resistance be not high, these defects seriously limit anti-corrosion, prevent
The barrier materials such as dirt are further applied concrete durability field.
In addition, concrete exterior wall decoration for vertical face material, over time, it may appear that wall is mouldy, stains, microorganism
(biodegradable order is aliphatic ester bond, peptide bond, urethane bond, aliphatic ehter bond and Asia for attachment, biodegrade and destruction
Methyl key) phenomena such as, so that surface is dirty, seriously affect building beauty and service life.Therefore, how research enhances protection
Material hydrophobic, biocidal property become antiseptic concrete field critical issue, and the research of this respect has become a heat in the field
Point.
The preparation of antifouling antibacterial sand, improves that current construction safety is more to be had in mind from concrete, avoids substrate Single-issue, can
So that protectiving scheme is richer.And fine sand particle surface is subjected to hydrophobically modified, obtaining has antifouling antibacterial husky mixed powder, has
Conducive to the hydrophobic uniformity of raising.Existing product and technology are improving waterproof performance, mainly carry out Morphological control, low on sand surface
Surface energy molecular layer cladding and modification etc., almost only consider hydrophobicity.Although hydrophobic surface is attached with centainly microorganism
Interception, but microbes are adsorbed in fault location, weak link first, are then survived, are bred, extension, simple hydrophobicity
Material is difficult to for a long time or complete inhibition microorganism attachment is stained and to organic protection coating degradation, and hydrophobicity is eventually gradually
It reduces or fails.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of antifouling antibacterial sand and preparation method thereof.It is provided by the invention
It is antifouling it is antibacterial it is husky there is excellent hydrophobic, antifouling, biocidal property, high production cost, the stability for solving such material is poor, substrate list
One the problems such as.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of antifouling antibacterial sand, comprising the following steps:
(1) by sand sieving, cleaning, the pretreatment grains of sand are obtained;
(2) the pretreatment grains of sand, alcoholic solvent and the cationic surface active agent mixing obtained the step (1), carries out
Modified-reaction obtains modified grains of sand suspension;
(3) tetraethoxysilane is added dropwise in the modification grains of sand suspension that the step (2) obtains, carries out polycondensation
Reaction, obtains the silica grains of sand;
(4) the silica grains of sand that the step (3) obtains are mixed with organic solvent, 4- bromobutanoylchloride and alkaline matter,
Acylation reaction is carried out, obtains being acylated the grains of sand;
(5) the acylation grains of sand, solvent, bifunctional group polymer and the alkaline matter mixing obtained the step (4),
Graft reaction is carried out, antifouling antibacterial sand is obtained;
Bifunctional group polymer is bis- with the long hydrocarbon chain of low-surface-energy and quaternary ammonium salt group, including N- in the step (5)
Alkyl, quaternized-PEI, the bis- alkyl of N-, alkyl includes the alkyl of carbon >=12 in quaternized-PEI.
Preferably, cationic surface active agent includes tetradecyltrimethylammonium bromide or 16 in the step (2)
Alkyl trimethyl ammonium bromide.
Preferably, the amount ratio of the pretreatment grains of sand, alcoholic solvent and cationic surface active agent is 5 in the step (2)
~15g:200mL:0.01~0.02mol.
Preferably, the amount ratio of tetraethoxysilane and the pretreatment grains of sand is 20mL:5~15g in the step (3).
Preferably, the amount ratio of the silica grains of sand, 4- bromobutanoylchloride and alkaline matter is 10~30g in the step (4):
2~6mL:0.001~0.009mol.
Preferably, the temperature of acylation reaction is 15~30 DEG C in the step (4), and the time is 12~14h.
Preferably, the mass ratio that the grains of sand and bifunctional group polymer are acylated in the step (5) is 2:1.
Preferably, 80~100 DEG C of temperature of graft reaction in the step (5), the time is 12~16h.
Preferably, the bis- alkyl of the N-, the preparation method of quaternized-PEI the following steps are included:
(I) by polyethyleneimine, K2CO3, tert-pentyl alcohol and brominated alkanes mixing after progress-alkylation, obtain N- alkyl-
PEI;Carbon number >=12 of the brominated alkanes;
(II) the N- alkyl-PEI that the step (I) obtains is mixed with dimethyl carbonate, carries out quaternization reaction, obtains
The bis- alkyl of N-, quaternized-PEI.
The present invention also provides the antifouling antibacterial sand that preparation method described in above-mentioned technical proposal obtains, the antifouling antibacterial sand
Surface has been grafted the dual functional polymer with the long hydrocarbon chain of low-surface-energy and with bactericidal quaternary ammonium salt groups by acyl group;It is described
The contact angle of antifouling antibacterial sand is 143~147 °;Sterilizing rate reaches 96~98%.
The present invention provides a kind of preparation methods of antifouling antibacterial sand, and sand is sieved, is cleaned, and it is husky to obtain pretreatment
Grain;The modified grains of sand are obtained by one layer of cationic surfactant of modified cladding first on the pretreatment grains of sand;Using polycondensation
Reaction connects one layer of silicon oxide layer on the modified grains of sand, obtains the silica grains of sand;The silica grains of sand are acylated, acyl is obtained
The base grains of sand;The grains of sand and the bis- alkyl of bifunctional group polymer N- are acylated, quaternized-PEI occurs graft reaction, obtains antifouling
Antibacterial sand.Antifouling antibacterial husky successively cladding silicon oxide layer and the bis- alkyl of dual functional polymer N- of the invention, it is-PEI layers quaternized,
With excellent hydrophobic performance and bacteriostasis property.From embodiment as can be seen that antifouling antibacterial husky contact angle provided by the invention >=
143 °, roll angle≤10 °, sterilizing rate is up to 96% or more.
Detailed description of the invention
Fig. 1 is the contact angle photo of the 1 antifouling antibacterial sand of gained of embodiment;
Fig. 2 is adhere to the test block of the antifouling antibacterial sand of the gained of embodiment 1 in sulfate reduction bacteria culture fluid 3 days surface shapes
Looks picture;
Fig. 3 is the antifouling antibacterial schematic diagram of antifouling antibacterial sand provided by the invention.
Specific embodiment
The present invention provides a kind of preparation methods of antifouling antibacterial sand, comprising the following steps:
(1) by sand sieving, cleaning, the pretreatment grains of sand are obtained;
(2) the pretreatment grains of sand, alcoholic solvent and the cationic surface active agent mixing obtained the step (1), carries out
Modified-reaction obtains modified grains of sand suspension;
(3) tetraethoxysilane is added dropwise in the modification grains of sand suspension that the step (2) obtains, carries out polycondensation
Reaction, obtains the silica grains of sand;
(4) the silica grains of sand that the step (3) obtains are mixed with organic solvent, 4- bromobutanoylchloride and alkaline matter,
Acylation reaction is carried out, obtains being acylated the grains of sand;
(5) the acylation grains of sand, solvent, bifunctional group polymer and the alkaline matter mixing obtained the step (4),
Graft reaction is carried out, antifouling antibacterial sand is obtained;
Bifunctional group polymer is bis- with the long hydrocarbon chain of low-surface-energy and quaternary ammonium salt group, including N- in the step (5)
Alkyl, quaternized-PEI, the bis- alkyl of N-, alkyl includes the alkyl of carbon >=12 in quaternized-PEI.
Sand is sieved, cleans by the present invention, obtains the pretreatment grains of sand.In the present invention, sieve used in the sieving
Aperture is preferably 50~300 μm, further preferably 90~200 μm, more preferably 100~150 μm.In the present invention, described
Cleaning preferably includes following steps: by the grains of sand after sieving through being cleaned by ultrasonic 5min, then successively using deionized water, dehydrated alcohol
Each cleaning 3~5 times obtains the pretreatment grains of sand.The present invention does not have special restriction to the source of sand, using those skilled in the art
Sand known to member, it is specific such as sand for building.
In the present invention, the sieving and cleaning, can be clean by greasiness removals such as the mud, the oil that are attached on sand, is
The reactions such as subsequent modification, absorption provide condition.
After obtaining the pretreatment grains of sand, the present invention mixes the pretreatment grains of sand, alcoholic solvent and cationic surface active agent
It closes, is modified reaction, obtain modified grains of sand suspension.In the present invention, the cationic surface active agent preferably includes
Tetradecyltrimethylammonium bromide or cetyl trimethylammonium bromide, more preferably cetyl trimethylammonium bromide.At this
In invention, the alcoholic solvent preferably includes dehydrated alcohol.In the present invention, the pretreatment grains of sand, alcoholic solvent and cationic
The amount ratio of surfactant is preferably 5~15g:200mL:0.01~0.02mol, further preferably 8~12g:200mL:
0.012~0.018mol, more preferably 9~11g:200mL:0.014~0.016mol.In the present invention, the modified-reaction
Temperature be preferably 15~30 DEG C, further preferably 20~25 DEG C;The time of the modified-reaction is preferably 1~2h.At this
In invention, the modified-reaction preferably carries out under stirring conditions.
After modified-reaction, it is 10~12 that modified-reaction product alkali is preferably adjusted pH value by the present invention, is modified
Grains of sand suspension.In the present invention, the alkali preferably includes ammonium hydroxide.The present invention is not special to the concentration and dosage of the ammonium hydroxide
Restriction, as long as product pH value 10~12 after modified-reaction can be made.
In the present invention, the surface modified reaction of the pretreatment grains of sand, in one layer of cationic of its adsorption
Activating agent stabilizes modified grains of sand surface so that modified sand surface has positive electricity, and the adjusting of modified grains of sand suspension pH value
Positive electricity performance lays the foundation for the subsequent silicon oxide layer that coats on the grains of sand.
After obtaining modified grains of sand suspension, tetraethoxysilane is added dropwise to the modified grains of sand suspension by the present invention
In, through polycondensation reaction, obtain the silica grains of sand.
In the present invention, the amount ratio of the tetraethoxysilane and the pretreatment grains of sand is preferably 20mL:5~15g, into one
Step is preferably 20mL:8~12g, more preferably 20mL:9~11g.In the present invention, the temperature of the polycondensation reaction is preferably 15
~30 DEG C, further preferably 20~25 DEG C;The time of the polycondensation reaction is preferably 7~9h.In the present invention, the polycondensation
Reaction preferably carries out under stirring conditions;The revolving speed of the stirring is preferably 60~240rpm, further preferably 90~
210rpm, more preferably 120~180rpm.
After polycondensation reaction, the present invention preferably stands the product of polycondensation reaction, removes supernatant;By gained sediment
It is washed with deionized 3~5 times, through drying, obtains the silica grains of sand.In the present invention, the temperature of the drying is preferably 50
~70 DEG C, the time is preferably 2~4 hours.
In the present invention, the tetraethoxysilane is added dropwise in modified grains of sand suspension, is inhaled first by molecule
It is attached to one layer of tetraethoxysilane of modified grains of sand adsorption, tetraethoxysilane forms silanol groups through hydrolysis;It is described
Silanol groups connect one layer of silicon oxide layer through polycondensation reaction, in the modified grains of sand, obtain the silica grains of sand;The cladding energy of silicon oxide layer
Enough enhance the integrality and fastness of grains of sand surface grafting dual functional polymer.
After obtaining the silica grains of sand, the present invention is by the silica grains of sand and organic solvent, 4- bromobutanoylchloride and basic species
Matter mixing, carries out acylation reaction, obtains being acylated the grains of sand.
In the present invention, the amount ratio of the silica grains of sand, 4- bromobutanoylchloride and alkaline matter is preferably 10~30g:2
~6mL:0.001~0.009mol, further preferably 15~25g:3~5mL:0.002~0.008mol, more preferably 18~
22g:4mL:0.003~0.006mol.In the present invention, the organic solvent preferably includes chloroform.The present invention is to described
The dosage of organic solvent does not have special restriction, and the silica grains of sand can be made to be completely dispersed.In the present invention, the alkalinity
Substance preferably includes potassium hydroxide.In the present invention, the effect of the alkaline matter is catalyst, can promote acylation reaction
Progress.
The present invention is to the hybrid mode of the silica grains of sand, organic solvent, 4- bromobutanoylchloride and alkaline matter without spy
Different restriction, using hybrid mode well known to those skilled in the art.
In the present invention, the temperature of the acylation reaction is preferably 15~30 DEG C, and further preferably 20~25 DEG C;Institute
The time for stating acylation reaction is preferably 12~14h.
After acylation reaction, the product of acylation reaction is preferably washed 3 with chloroform, methanol respectively by the present invention
~5 times, remove remaining 4- bromobutanoylchloride;Then it is dried in vacuo 2~4 hours in 50~70 DEG C, obtains the acylation grains of sand.
In the present invention, acylation reaction can be in the area load acyl group of the silica grains of sand, to load bifunctional group
Polymer provides linking group and condition.
It obtains after being acylated the grains of sand, the present invention is by the acylation grains of sand, solvent, bifunctional group polymer and basic species
Matter mixing, carries out graft reaction, obtains antifouling antibacterial sand.
In the present invention, the grains of sand and the mass ratio of dual functional polymer of being acylated are preferably 2:1.In the present invention,
The solvent preferably includes dimethylformamide.The present invention does not have special restriction to the dosage of the dimethylformamide, only
, which can make to be acylated the grains of sand, is uniformly dispersed.In the present invention, the alkaline matter preferably includes potassium hydroxide.The present invention
Concentration and dosage to the potassium hydroxide do not have special restriction, as long as can make pH value > 8 of graft reaction.
In the present invention, the bifunctional group polymer has the long hydrocarbon chain of low-surface-energy and quaternary ammonium salt group.In this hair
In bright, the bifunctional group polymer includes the bis- alkyl of N-, quaternized-PEI, the bis- alkyl of N-, alkane in quaternized-PEI
Base includes the alkyl of carbon >=12.In the present invention, the bis- alkyl of the N-, quaternized-PEI preferably include N- dodecyl, N- first
Base, quaternized-PEI, N- tridecyl, N- methyl, quaternized-PEI, N- myristyl, N- methyl, quaternized-PEI, N- ten
Five alkyl, N- methyl, quaternized-PEI, N- cetyl, N- methyl, quaternized-PEI, N- octadecyl, N- methyl, quaternary ammonium
Change-PEI or N- dodecyl, N- ethyl, quaternized-PEI.
In the present invention, the bis- alkyl of the N-, quaternized-PEI are preferably prepared by following steps:
(I) by polyethyleneimine, K2CO3, tert-pentyl alcohol and brominated alkanes mixing after be alkylated, obtain N- alkyl-PEI;
Carbon number >=12 of the brominated alkanes;
(II) the N- alkyl-PEI that the step (I) obtains is mixed with dimethyl carbonate, carries out quaternization reaction, obtains
The bis- alkyl of N-, quaternized-PEI.
The present invention is in the preparation bis- alkyl of N-, quaternized-PEI, preferably by polyethyleneimine, K2CO3, tert-pentyl alcohol and bromo
It is alkylated after alkane mixing, obtains N- alkyl-PEI;Carbon number >=12 of the brominated alkanes.In the present invention, described
Brominated alkanes preferably include bromododecane, tridecane bromide, bromotetradecane, bromo pentadecane, bromohexadecane or bromo
Octadecane.In the present invention, the polyethyleneimine, K2CO3, tert-pentyl alcohol and brominated alkanes amount ratio be preferably 5~7g:20
~25g:60~80mL:80~110mL, further preferably 5.5~6.5g:20.5~24g:65~75mL:85~105mL,
More preferably 5.5g:21~22g:70mL:90~100mL.The present invention is to the polyethyleneimine, K2CO3, tert-pentyl alcohol and bromo
The hybrid mode of alkane does not have special restriction, using hybrid mode well known to those skilled in the art.
In the present invention, the temperature of the alkylated reaction is preferably 80~100 DEG C, and further preferably 90~98 DEG C,
More preferably 95 DEG C.In the present invention, the time of the alkylated reaction is preferably 96~120h, further preferably 98~
115h, more preferably 100~110h.
After alkylated reaction, the present invention preferably filters the product of alkylated reaction, obtains N- alkyl-PEI.
After obtaining N- alkyl-PEI, the present invention preferably mixes N- alkyl-PEI with dimethyl carbonate, carries out quaternized anti-
It answers, obtains the bis- alkyl of N-, quaternized-PEI.In the present invention, the molar ratio of the dimethyl carbonate and N- alkyl-PEI is preferred
For 5:1.In the present invention, the temperature of the quaternization reaction is preferably 125~130 DEG C, and further preferably 126~129 DEG C,
More preferably 127~128 DEG C;The pressure of the quaternization reaction is preferably 2.7~3MPa, further preferably 2.8~
2.9MPa;The time of the quaternization reaction is preferably 24~32h, further preferably 25~30h, more preferably 26~28h.
In the present invention, the quaternization reaction preferably carries out in the presence of stirring and protective gas.
After quaternization reaction, the product of quaternization reaction is preferably cooled to room temperature by the present invention, in Rotary Evaporators
In in 45~55 DEG C of 3~5h of vacuum distillation, obtain the bis- alkyl of N-, quaternized-PEI;The methanol and dimethyl carbonate distilled out is mixed
It closes liquid and condensing recovery is carried out by condenser.
In the present invention, alkyl carbon number >=12 in N- alkyl-PEI, so that N- alkyl-PEI is in quaternization reaction,
Long alkane chain drop low-surface-energy could be relied on, guarantees the bis- alkyl of N-, the hydrophobic effect of quaternized-PEI;Meanwhile having excellent
Bactericidal effect.
The present invention does not have the hybrid mode of the acylation grains of sand, solvent, bifunctional group polymer and alkaline matter
Special restriction, using hybrid mode well known to those skilled in the art.
In the present invention, the temperature of the graft reaction is preferably 80~100 DEG C, and further preferably 85~95 DEG C, more
Preferably 90 DEG C;The time of the graft reaction is preferably 12~16h, further preferably 13~15h, more preferably 14h.
After graft reaction, the present invention preferably filters the product of graft reaction;Sediment is washed 2~4 with methanol
It is secondary;In 50~70 DEG C of 2~4h of vacuum drying, antifouling antibacterial sand is obtained.
In the present invention, one layer of silicon oxide layer is successively coated on grains of sand surface and dual-functional group with low-surface-energy is reunited
Nitride layer is closed, ensure that antifouling antibacterial the hydrophobic of sand, soil resistance and antibiotic property.
The present invention also provides the antifouling antibacterial sand that preparation method described in above-mentioned technical proposal obtains.It is provided by the invention anti-
Dirty antibacterial husky surface has been grafted difunctional poly- with the long hydrocarbon chain of low-surface-energy and with bactericidal quaternary ammonium salt groups by acyl group
Close object;The contact angle of the antifouling antibacterial sand is 143~147 °;Sterilizing rate reaches 96~98%.
Antifouling antibacterial sand provided by the invention and preparation method thereof is described in detail below with reference to embodiment, still
They cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.14mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 1h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 12, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in the modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, and after polycondensation reaction, the product of polycondensation reaction is stood into removal supernatant;It will
Sediment is washed with deionized 3 times, and dry 4h, obtains the silica grains of sand at 60 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 3h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) the 20g acylation grains of sand are distributed in dimethyl formamide solution, add 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will connect
Branch reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21gK2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C into
Row alkylated reaction 100h, is filtered, and N- dodecyl-PEI is obtained;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 128 DEG C, 2.8MPa;By season
The product of ammoniumization reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N-
Methyl, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
The contact angle of antifouling antibacterial sand obtained by the present embodiment is tested, picture is as described in Figure 1.It will be seen from figure 1 that this implementation
The contact angle of the antifouling antibacterial sand of example gained is 147 °.
Building sand is modified according to the present embodiment step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N-, quaternized methyl-PEI replace with the N- dodecyl-PEI that step (I) obtains;Obtained product
It is named as building sand+N- dodecyl-PEI;
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and the present embodiment is adhered in test block,
The test block for being stained with the grains of sand is cultivated 3 days in sulfate reducing bacteria, observes antibiotic property, contact angle and the rolling of above-mentioned three kinds of grains of sand
Dynamic angle, the results are shown in Table 1.As can be seen from Table 1: antifouling antibacterial sand manufactured in the present embodiment has preferable hydrophobicity simultaneously
Higher sterilizing rate.
The performance test results of 1 three kinds of grains of sand of table
Adhering to the test blocks of the antifouling antibacterial grains of sand obtained by the present embodiment, 3 days surface topographies are such as in sulfate reduction bacteria culture fluid
Shown in Fig. 2.As can be seen from Figure 2: antifouling antibacterial husky surface cleaning and inanimate object, organic debris etc. manufactured in the present embodiment are viscous
It is attached, there is excellent antifouling biocidal property.
Fig. 3 is the antifouling antibacterial schematic diagram of antifouling antibacterial sand provided by the invention.From figure 3, it can be seen that the present invention provides
Antifouling antibacterial husky there is excellent hydrophobicity and biocidal property.
Embodiment 2
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.16mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 2h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 12, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in above-mentioned modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, after polycondensation reaction, the product of polycondensation reaction is stood, removal supernatant;
Sediment is washed with deionized 3 times, dry 4h, obtains the silica grains of sand at 60 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1.5mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 4h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) 20g acylation particle is distributed in dimethyl formamide solution, adds 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1.5mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will
Graft reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21gK2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C into
Row alkylated reaction 96h, is filtered, and N- dodecyl-PEI is obtained;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 130 DEG C, 2.8MPa;By season
The product of ammoniumization reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N-
Methyl, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
Building sand is modified according to the present embodiment step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N- methyl-PEI replaces with the N- dodecyl-PEI that step (I) obtains;Obtained product, which is named as, to be built
Build sand+N- dodecyl-PEI.
Contact angle result such as 2 institute of table of antifouling antibacterial sand obtained by the present embodiment is tested using method same as Example 1
Show.
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and the present embodiment is adhered in test block,
There is the test block of the grains of sand to cultivate in sulfate reducing bacteria 3 days viscosity, observe the antibiotic property of above-mentioned three kinds of grains of sand, as a result such as table 2
It is shown.As can be seen from Table 2: antifouling antibacterial sand manufactured in the present embodiment has preferable hydrophobicity and higher sterilizing rate simultaneously.
The performance test results of 2 three kinds of grains of sand of table
Embodiment 3
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.15mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 2h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 12, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in above-mentioned modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, after polycondensation reaction, the product of polycondensation reaction is stood, removal supernatant;
Sediment is washed with deionized 3 times, dry 4h, obtains the silica grains of sand at 65 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 4h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) 20g acylation particle is distributed in dimethyl formamide solution, adds 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1.5mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will
Graft reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21g K2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C
It is alkylated reaction 100h, is filtered, obtains N- dodecyl-PEI;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 130 DEG C, 2.8MPa;By season
The product of ammoniumization reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N-
Methyl, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
Building sand is modified according to the present embodiment step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N- methyl-PEI replaces with the N- dodecyl-PEI that step (I) obtains;Obtained product, which is named as, to be built
Build sand+N- dodecyl-PEI.
Contact angle result such as 3 institute of table of antifouling antibacterial sand obtained by the present embodiment is tested using method same as Example 1
Show.
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and the present embodiment is adhered in test block,
There is the test block of the grains of sand to cultivate in sulfate reducing bacteria 3 days viscosity, observe the antibiotic property of above-mentioned three kinds of grains of sand, as a result such as table 3
It is shown.As can be seen from Table 3: antifouling antibacterial sand manufactured in the present embodiment has preferable hydrophobicity and higher sterilizing rate simultaneously.
The performance test results of 3 three kinds of grains of sand of table
Comparative example 1
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.05mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 1h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 12, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in the modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, and after polycondensation reaction, the product of polycondensation reaction is stood into removal supernatant;It will
Sediment is washed with deionized 3 times, and dry 4h, obtains the silica grains of sand at 60 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 3h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) the 20g acylation grains of sand are distributed in dimethyl formamide solution, add 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will connect
Branch reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21gK2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C into
Row alkylated reaction 100h, is filtered, and N- dodecyl-PEI is obtained;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 128 DEG C, 2.8MPa;By season
The product of ammoniumization reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N-
Methyl, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
Building sand is modified according to this comparative example step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N- methyl, quaternized-PEI replaces with the N- dodecyl-PEI that step (I) obtains;Obtained product
It is named as building sand+N- dodecyl-PEI.
Contact angle result such as 4 institute of table of antifouling antibacterial sand obtained by this comparative example is tested using method same as Example 1
Show.
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and this comparative example is adhered in test block,
There is the test block of the grains of sand to cultivate in sulfate reducing bacteria 3 days viscosity, observe the antibiotic property of above-mentioned three kinds of grains of sand, as a result such as table 4
It is shown.As can be seen from Table 4: the antifouling antibacterial sand of this comparative example preparation has low hydrophobicity and lower sterilizing rate.
The performance test results of 4 three kinds of grains of sand of table
Comparative example 2
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.14mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 1h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 8, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in the modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, and after polycondensation reaction, the product of polycondensation reaction is stood into removal supernatant;It will
Sediment is washed with deionized 3 times, and dry 4h, obtains the silica grains of sand at 60 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 3h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) the 20g acylation grains of sand are distributed in dimethyl formamide solution, add 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will connect
Branch reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21gK2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C into
Row alkylated reaction 100h, is filtered, and N- dodecyl-PEI is obtained;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 128 DEG C, 2.8MPa;By season
The product of ammoniumization reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N-
Methyl, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
Building sand is modified according to this comparative example step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N- methyl-PEI replaces with the N- dodecyl-PEI that step (I) obtains;Obtained product, which is named as, to be built
Build sand+N- dodecyl-PEI.
Contact angle result such as 5 institute of table of antifouling antibacterial sand obtained by this comparative example is tested using method same as Example 1
Show.
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and this comparative example is adhered in test block,
There is the test block of the grains of sand to cultivate in sulfate reducing bacteria 3 days viscosity, observe the antibiotic property of above-mentioned three kinds of grains of sand, as a result such as table 5
It is shown.As can be seen from Table 5: the preparation of this comparative example it is antifouling it is antibacterial it is husky there is certain hydrophobicity and sterilizing rate, but performance
It is lower.
The performance test results of 5 three kinds of grains of sand of table
Comparative example 3
A kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) sand will be built, deionization is successively used in be sieved (100~150 μm of the aperture of sieve), ultrasonic cleaning 5min
Water, washes of absolute alcohol 3 times, it is dry, obtain the pretreatment grains of sand;
(2) 10g is pre-processed into the cetyl front three that the grains of sand, 200mL dehydrated alcohol and 100mL concentration are 0.14mol/L
The aqueous solution of base ammonium bromide mixes, and is modified under conditions of stirring and room temperature and reacts 1h, after modified-reaction, uses ammonium hydroxide
The pH value of the product of modified-reaction is adjusted to 12, obtains modified grains of sand suspension;
(3) 20mL tetraethoxysilane is added dropwise in the modified grains of sand suspension, is in speed of agitator
Polycondensation reaction 8h is carried out under conditions of 150rpm, and after polycondensation reaction, the product of polycondensation reaction is stood into removal supernatant;It will
Sediment is washed with deionized 3 times, and dry 4h, obtains the silica grains of sand at 60 DEG C;
(4) the 20g silica grains of sand are dispersed in 80mL chloroform, are with 4mL 4- bromobutanoylchloride, 1mL concentration
The potassium hydroxide aqueous solution of 3mol/L mixes, and carries out acylation reaction 12h at room temperature;The product of acylation reaction is filtered,
Sediment is washed 3 times with chloroform, methanol respectively, 3h is dried in vacuo at 65 DEG C, obtains the acylation grains of sand;
(5) the 20g acylation grains of sand are distributed in dimethyl formamide solution, add 10g N- dodecyl, N- first
The potassium hydroxide aqueous solution that base, quaternized-PEI and 1mL concentration are 3mol/L mixes, in 90 DEG C of progress graft reaction 12h;It will connect
Branch reaction product filters, and sediment is washed 3 times with methanol, in 65 DEG C of vacuum drying 4h, obtains the antifouling antibacterial grains of sand.
Wherein, the preparation method of N- dodecyl, N- methyl, quaternized-PEI preferably includes following steps:
(I) by 5.5g polyethyleneimine, 21gK2CO3, 70mL tert-pentyl alcohol and 90mL bromododecane mixing, at 95 DEG C into
Row alkylated reaction 100h, is filtered, and N- dodecyl-PEI is obtained;
(II) by dimethyl carbonate and N- dodecyl-PEI, 5:1 is mixed and is placed in autoclave in molar ratio, uses nitrogen
Internal oxygen is displaced, quaternization reaction 26h is carried out under conditions of speed of agitator is 180rpm, 128 DEG C, normal pressure;By quaternary ammonium
The product for changing reaction is cooled to room temperature, and is carried out vacuum distillation 3h in Rotary Evaporators at 50 DEG C, is obtained N- dodecyl, N- first
Base, quaternized-PEI;The methanol and dimethyl carbonate mixed liquor distilled out carries out condensing recovery by condenser.
Building sand is modified according to this comparative example step (1)~(5) method, difference is only that, by step (5)
In N- dodecyl, N- methyl-PEI replaces with the N- dodecyl-PEI that step (I) obtains;Obtained product, which is named as, to be built
Build sand+N- dodecyl-PEI.
Contact angle result such as 6 institute of table of antifouling antibacterial sand obtained by this comparative example is tested using method same as Example 1
Show.
The antifouling antibacterial sand for building sand, building sand+N- dodecyl-PEI and this comparative example is adhered in test block,
There is the test block of the grains of sand to cultivate in sulfate reducing bacteria 3 days viscosity, observe the antibiotic property of above-mentioned three kinds of grains of sand, as a result such as table 6
It is shown.As can be seen from Table 6: the antifouling antibacterial sand of this comparative example preparation has preferable hydrophobicity, while having bactericidal properties, but
It is that sterilizing rate is lower.
The performance test results of 6 three kinds of grains of sand of table
Comparative example 1~3 and comparative example 1~3 it can be seen that in the present invention certain experiment parameters and condition can determine or
Influence the functionality of the modification of grains of sand surface and subsequent graft polymers, the final performance for influencing gained grains of sand product.Three comparisons
Respectively at three cationic surfactant concentration, reacting solution pH value, quaternization reaction pressure aspects beyond the present invention in example
Preferred scope eventually leads to the failure for preparing antifouling antibacterial sand.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of antifouling antibacterial sand, comprising the following steps:
(1) by sand sieving, cleaning, the pretreatment grains of sand are obtained;
(2) the pretreatment grains of sand, alcoholic solvent and the cationic surface active agent mixing obtained the step (1), is modified
Reaction obtains modified grains of sand suspension;
(3) tetraethoxysilane is added dropwise in the modification grains of sand suspension that the step (2) obtains, it is anti-carries out polycondensation
It answers, obtains the silica grains of sand;
(4) the silica grains of sand that the step (3) obtains are mixed with organic solvent, 4- bromobutanoylchloride and alkaline matter, is carried out
Acylation reaction obtains being acylated the grains of sand;
(5) the acylation grains of sand, solvent, bifunctional group polymer and the alkaline matter mixing obtained the step (4), carries out
Graft reaction obtains antifouling antibacterial sand;
Bifunctional group polymer has the long hydrocarbon chain of low-surface-energy and quaternary ammonium salt group, including the bis- alkyl of N- in the step (5),
Quaternized-PEI, the bis- alkyl of N-, alkyl includes the alkyl of carbon >=12 in quaternized-PEI.
2. preparation method according to claim 1, which is characterized in that cationic surface active agent in the step (2)
Including tetradecyltrimethylammonium bromide or cetyl trimethylammonium bromide.
3. preparation method according to claim 1 or 2, which is characterized in that the pretreatment grains of sand, alcohol are molten in the step (2)
The amount ratio of agent and cationic surface active agent is 5~15g:200mL:0.01~0.02mol.
4. preparation method according to claim 1, which is characterized in that tetraethoxysilane and pre- place in the step (3)
The amount ratio for managing the grains of sand is 20mL:5~15g.
5. preparation method according to claim 1, which is characterized in that the silica grains of sand, 4- bromine butyryl in the step (4)
The amount ratio of chlorine and alkaline matter is 10~30g:2~6mL:0.001~0.009mol.
6. preparation method according to claim 1 or 5, which is characterized in that the temperature of acylation reaction in the step (4)
It is 15~30 DEG C, the time is 12~14h.
7. preparation method according to claim 1, which is characterized in that be acylated the grains of sand and difunctional in the step (5)
The mass ratio of radical polymerisation object is 2:1.
8. preparation method according to claim 1 or claim 7, which is characterized in that the temperature 80 of graft reaction in the step (5)
~100 DEG C, the time is 12~16h.
9. preparation method according to claim 1, which is characterized in that the bis- alkyl of N-, the preparation side of quaternized-PEI
Method the following steps are included:
(I) by polyethyleneimine, K2CO3, tert-pentyl alcohol and brominated alkanes mixing after be alkylated, obtain N- alkyl-PEI;It is described
Carbon number >=12 of brominated alkanes;
(II) the N- alkyl-PEI that the step (I) obtains is mixed with dimethyl carbonate, carries out quaternization reaction, it is bis- obtains N-
Alkyl, quaternized-PEI.
10. the antifouling antibacterial sand that any one of claim 1~9 preparation method obtains, which is characterized in that described antifouling antibacterial
Husky surface has been grafted the dual functional polymer with the long hydrocarbon chain of low-surface-energy and with bactericidal quaternary ammonium salt groups by acyl group;Institute
The contact angle for stating antifouling antibacterial sand is 143~147 °;Sterilizing rate reaches 96~98%.
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