CN102990740A - Nano composite wood preservative and preparation method thereof - Google Patents
Nano composite wood preservative and preparation method thereof Download PDFInfo
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- CN102990740A CN102990740A CN2012103425752A CN201210342575A CN102990740A CN 102990740 A CN102990740 A CN 102990740A CN 2012103425752 A CN2012103425752 A CN 2012103425752A CN 201210342575 A CN201210342575 A CN 201210342575A CN 102990740 A CN102990740 A CN 102990740A
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Abstract
The invention discloses a nano composite wood preservative and a preparation method thereof. According to the nano composite wood preservative, a silica nanometer material is adopted as a carrier for carrying out surface grafting on polymer ammonium and amine, and the amine is adopted and used for chelating copper ions. The preparation method comprises the steps of modifying the surface of the silica nanometer material, grafting polyethyleneimine to the surface-modified silica nanometer material, synthesizing a QPEI (Quaternary Polyethyleneimine)/SiO2 nanometer material, synthesizing a PEI (Polyetherimide)-QPEI/SiO2 nanometer material, and chelating the copper ion. The nano composite wood preservative hardly runs off from the wood, is higher in sterilizing effect, and can reduce the pollution of the massively-lost preservative to the environment.
Description
Technical field
The present invention relates to the preservative technology field, relate in particular a kind of nano combined timber preservative and preparation method thereof.
Background technology
Timber preservative comprises that mainly oils anticorrisive agent, oil carry anticorrisive agent and water ballast anticorrisive agent three classes, and at present the most widely used is waterborne-type preservation.Waterborne-type preservation mainly contains: copper chromium arsenic (CCA), copper chromium boron (CCB), fluorine chromium phenol arsenic (FCAP), ammonical copper arsenite (ACA), acid copper chromate Ah (ACC) etc.The waterborne-type preservation price is low, effective, in recent years, these anticorrisive agents are widely applied, such anticorrisive agent is the main anticorrisive agent of for building and home-use material of the overwhelming majority, but anticorrisive agent easily runs off in the preserving timber use procedure, and the compounds such as the chromium that runs off, arsenic, copper also can be to soil, water resource and environment.
The molten alkyl cuprammonium of ammonia (ACQ) is one of waterborne-type preservation that sales volume is larger in the market, and this anticorrisive agent avoids chromium and arsenic violent in toxicity to the pollution of environment, but easily not yet solves from the problem that timber runs off for ammonium salt and mantoquita.Along with the fast development of nanometer technology, nano anti-biotic material is a class novel antibacterial material of developing in recent years.The timber that has bibliographical information to process with nano zine oxide has certain preservative efficacy, and nano material is difficult for running off from timber.But this material is not very strong owing to do not introduce the sterilizing function group to the ability that prevents fungi erosion timber.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nano combined timber preservative and preparation method thereof, this anticorrisive agent is difficult for running off from timber, and has higher biocidal efficacies.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of nano combined timber preservative, its structural representation formula is:
In the formula:
Be nanometer SiO
2,
Be PEI,
Be QPEI,
Be Cu
2+
A kind of preparation method of nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: silica nano material is dispersed in the alcohol, measure an amount of γ-chloropropyl triethoxysilane, add in the reaction vessel, stir, be heated to more than the pure boiling point, constant temperature back flow reaction 8 ~ 12 h make chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with alcohol, the product after the washing is dry to be processed, and obtains the silica nano material of chloropropylation, i.e. CP/SiO
2Nano material; The mass ratio of described silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:(0.5 ~ 1): (6 ~ 8), described silica nano material granularity is 90 ~ 150nm, described freeze-day with constant temperature temperature is 100 ~ 150 ℃, and be 12 ~ 24 h drying time;
The silica nano material grafting polyethylene imine of B, surface modification, polymine is abbreviated as PEI: the silica nano material of chloropropylation is distributed in the water, add an amount of PEI, mixed liquor is heated, back flow reaction, reaction finish rear to the reactant liquor centrifugation, and washing sample, remove residual PEI, obtain PEI/SiO after the drying
2Nano material; Described back flow reaction condition is: 90 ~ 100 ℃ of back flow reaction 10 ~ 12 h, and the silica nano material of described surface modification, the PEI concentration in mixed liquor is respectively: 0.1 ~ 0.15 g/g and 0.2 ~ 0.3 g/g; Baking temperature is 60 ~ 100 ℃, and be 6 ~ 12 h drying time;
C, QPEI/SiO
2Synthesizing of nano material, QPEI refers to quaternised PEI: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, stirs to be warming up to more than the expoxy propane boiling point after lower ice bath reacts 6 ~ 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, under 50 ~ 70 ℃, carry out back flow reaction 18 ~ 24 h, after reaction finishes, filter, with alcohol washing product, drying namely gets QPEI/SiO
2Material; Described PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:(4 ~ 6), the PEI/SiO of described alcohol, tertiary amine
2,, benzyl chloride mass ratio be (2 ~ 3): 1:(1 ~ 2); Described drying condition is that 60 ~ 100 ℃ of lower dryings are more than 24;
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the alcohol, adds an amount of γ-chloropropyl triethoxysilane, is heated to more than the pure boiling point constant temperature stirring and refluxing reaction 8 ~ 12 h, centrifugation, drying; Intermediate product after the drying is dispersed in the PEI aqueous solution, at 80 ~ 100 ℃ of lower constant temperature stirring and refluxing reaction 12 ~ 24h, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material; Described QPEI/SiO
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:(6 ~ 10): (0.5 ~ 1), drying condition is: 60 ~ 100 ℃, be 12 ~ 24 h drying time; The mass ratio of described intermediate product, PEI, water is: 1:(3 ~ 5): (8 ~ 12);
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating; Described PEI-QPEI/SiO
2The mass ratio of nano material, copper sulphate, water is: 1:(0.5 ~ 1): (6 ~ 8).
Single nanometer silicon dioxide particle can react with several organic molecules, some polymer chains of participating in reaction in the above reaction equation.
Alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, the ethylene glycol among described steps A, C, the D.
Silica nano material can prepare by the following method in the described steps A:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor;
(2), add an amount of ethyl orthosilicate (TEOS) in the mixed liquor, 10 ~ 40 ℃ of reaction 6 ~ 10 h leave standstill centrifugation after a period of time with reactant liquor, drying makes silica nano material.
Alcohol, water, ammonia (NH in the described step (1)
3) mass ratio be (50 ~ 70): (8 ~ 10): 0.5, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.025 ~ 0.03 g/g in the step (2), drying condition is 50 ~ 90 ℃ of drying 6 ~ 10 h.
The present invention's silica nano material is that carrier carries out surface grafting polymeric ammonium and amine, utilize amine chelated copper ion, make and have stable performance, avirulence, nonirritant and use safety and high-quality immobilization timber preservative, relatively concentrate the preservative efficacy that has strengthened this material by functional group at nano-material surface, be mixed with heavy metal ion or little molecule quaternary ammonium salt and mantoquita with traditional timber preservative and form ratio, and product of the present invention is to utilize function silica nano material and chelated copper ion to be prepared from, solidification has avoided traditional preservatives to be easy to the shortcoming that runs off from timber, and functional group is concentrated the preservative efficacy that has also strengthened this material relatively at nano-material surface, the nano combined timber preservative of the present invention is difficult for running off from timber, and has higher biocidal efficacies, the environmental pollution that a large amount of losses of minimizing anticorrisive agent cause.
Description of drawings:
Fig. 1 is the infrared spectrum of the nanostructure intermediate of the embodiment of the invention 1 preparation.
Among the figure: 1, the infrared spectrum of silica nano material; 2, CP/SiO
2The infrared spectrum of nano material; 3, PEI/SiO
2The infrared spectrum of nano material; 4, QPEI/SiO
2The infrared spectrum of nano material; 5, PEI-QPEI/SiO
2The infrared spectrum of nano material.
The specific embodiment
Embodiment 1
A kind of nano combined timber preservative, its structural representation formula is:
In the formula:
Be nanometer SiO
2,
Be PEI,
Be QPEI,
Be Cu
2+
A kind of preparation method of nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: be that the silica of 100 nm is dispersed in the methyl alcohol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating at 66 ℃ of constant temperature back flow reaction 8 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with methyl alcohol, 100 ℃ of drying 12 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The reaction equation of steps A is as follows:
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.1 g/g and 0.2 g/g, mixed liquor is heated, at 90 ℃ of lower back flow reaction 10 h, reaction finishes rear to the reactant liquor centrifugation, and uses the methanol wash sample, remove residual PEI, obtain PEI/SiO behind 60 ℃ of drying 6 h
2Nano material;
The reaction equation of step B is as follows:
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:4, stirs to be warming up to 35 ℃ after lower ice bath reacts 6 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of methyl alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of methyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 2:1:1; Carry out back flow reaction 18 h under 50 ℃, after reaction finishes, filter, use the methanol wash product, 80 ℃ of lower dry 24 h namely get QPEI/SiO
2Material;
The reaction equation of step C is as follows:
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the methyl alcohol, adds an amount of γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:6:0.5, is heated to 66 ℃, and stirring and refluxing is reacted 8 h, centrifugation, 100 ℃ of drying 12 h; Intermediate product after the drying is dispersed in the PEI aqueous solution, and wherein the mass ratio of intermediate product, PEI, water is: 1:3:8; React 12 h 90 ℃ of lower constant temperature stirring and refluxing, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material;
The reaction equation of step D is as follows:
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating; Described PEI-QPEI/SiO
2The mass ratio of nano material, copper sulphate, water is: 1:0.5:6.
The reaction equation of step e is as follows:
The infrared spectrum of the nanostructure intermediate of embodiment 1 preparation is seen Fig. 1, sees that from figure each intermediate is at 1083 cm
-1There is an extremely strong wide absworption peak at the place.The corresponding SiO in this peak
2The stretching vibration absworption peak of middle Si-O-Si.At 3431 cm
-1The broad peak at place is the absworption peak relevant with the silicon hydroxyl that forms hydrogen bond and adsorbed water, and after chemical modification, this peak weakens to some extent, and at 2953 cm
-1C-H key chattering absworption peak appears in the place, shows nanometer SiO
2Chloropropylation has been realized on the surface, strengthens gradually by 2-5 by can be observed C-H key chattering absworption peak among the figure, and this is because intermediate C-H key in grafting PEI and quaternized process increases gradually.Chloropropylation SiO
2With among the figure after the PEI reaction 3,4,5 at 1460 cm
-1C-N key stretching vibration absworption peak appears in the place, shows that PEI successfully is grafted to nanometer SiO
2The surface.By among the figure 4,5 observe sample quaternized after at 1627,1417,696,758 cm
-1The phenyl ring characteristic absorption peak occurs, show that quaterisation has occured the PE I that is grafted on the silica gel, has formed functional material QPEI/SiO
2Therefore quaternary ammonium salt does not have INFRARED ABSORPTION, corresponding absworption peak do not occur in 4,5 in the drawings.By among the figure 5 observe sample again behind the grafting PEI at 1460 cm
-1The C that the place occurs-N key stretching vibration absworption peak strengthens in 4 among the figure, this show PEI successful again be grafted to QPEI/SiO
2Nano-material surface.
A kind of nano combined timber preservative, its structural representation formula is with embodiment 1;
A kind of preparation method of nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: be that the silica of 120nm is dispersed in the ethanol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating at 80 ℃ of constant temperature back flow reaction 10 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with methyl alcohol, 120 ℃ of drying 15 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.12 g/g and 0.25 g/g, mixed liquor is heated, at 90 ℃ of lower back flow reaction 12 h, reaction finishes rear to the reactant liquor centrifugation, and uses the ethanol washing sample, remove residual PEI, obtain PEI/SiO behind 80 ℃ of drying 10 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:5, stirs to be warming up to 35 ℃ after lower ice bath reacts 8 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of ethanol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of ethanol, tertiary amine
2,, benzyl chloride mass ratio be 2.5:1:1.5; Carry out back flow reaction 20 h under 60 ℃, after reaction finishes, filter, use the ethanol washed product, 80 ℃ of lower dry 28 h namely get QPEI/SiO
2Material;
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the ethanol, adds an amount of γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:8:0.8, is heated to 80 ℃, and stirring and refluxing is reacted 10 h, centrifugation, 80 ℃ of drying 10 h; Intermediate product after the drying is dispersed in the PEI aqueous solution, and wherein the mass ratio of intermediate product, PEI, water is: 1:4:10; React 15 h 90 ℃ of lower constant temperature stirring and refluxing, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material;
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating; Described PEI-QPEI/SiO
2The mass ratio of nano material, copper sulphate, water is: 1:0.8:7.
The reaction equation of steps A ~ E is with embodiment 1;
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 50:8:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 10 ℃ of reaction 10 h leave standstill centrifugation after a period of time, 50 ℃ of drying 10 h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.025 g/g.
A kind of nano combined timber preservative, its structural representation formula is with embodiment 1;
A kind of preparation method of nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: be that the silica of 150nm is dispersed in the propyl alcohol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating at 88 ℃ of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with propyl alcohol, 150 ℃ of drying 18 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.15 g/g and 0.3 g/g, mixed liquor is heated, at 100 ℃ of lower back flow reaction 10 h, reaction finishes rear to the reactant liquor centrifugation, and uses the propyl alcohol washing sample, remove residual PEI, obtain PEI/SiO behind 100 ℃ of drying 10 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:6, stirs to be warming up to 35 ℃ after lower ice bath reacts 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of propyl alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of propyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 3:1:2; Carry out back flow reaction 24 h under 70 ℃, after reaction finishes, filter, use the propyl alcohol washed product, 100 ℃ of lower dry 24 h namely get QPEI/SiO
2Material;
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the propyl alcohol, adds an amount of γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:10:1, is heated to 88 ℃, and stirring and refluxing is reacted 12 h, centrifugation, 100 ℃ of drying 18 h; Intermediate product after the drying is dispersed in the PEI aqueous solution, and wherein the mass ratio of intermediate product, PEI, water is: 1:5:12; At 100 ℃ of lower constant temperature stirring and refluxing reaction 12h, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material;
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating; Described PEI-QPEI/SiO
2The mass ratio of nano material, copper sulphate, water is: 1:1:8.
The reaction equation of steps A ~ E is with embodiment 1;
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 60:9:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 40 ℃ of reaction 6 h leave standstill centrifugation after a period of time, 80 ℃ of drying 8 h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.028 g/g.
A kind of nano combined timber preservative, its structural representation formula is with embodiment 1;
A kind of preparation method of nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: be that the silica of 110 nm is dispersed in the ethylene glycol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating at 198 ℃ of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and spent glycol advances washing, 150 ℃ of drying 24 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.12 g/g and 0.3 g/g, mixed liquor is heated, at 100 ℃ of lower back flow reaction 12 h, reaction finishes rear to the reactant liquor centrifugation, and the spent glycol washing sample, remove residual PEI, obtain PEI/SiO behind 100 ℃ of drying 12 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:6, stirs to be warming up to 36 ℃ after lower ice bath reacts 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2Proper amount of glycol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of propyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 3:1:2; Under 70 ℃, carry out back flow reaction 24 h, after reaction finishes, filter, the spent glycol washed product, 60 ℃ of lower dry 30 h namely get QPEI/SiO
2Material;
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the ethylene glycol, adds an amount of γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:10:1, is heated to 198 ℃, and stirring and refluxing is reacted 12 h, centrifugation, 60 ℃ of drying 24 h; Intermediate product after the drying is dispersed in the PEI aqueous solution, and wherein the mass ratio of intermediate product, PEI, water is: 1:5:12; React 24 h 80 ℃ of lower constant temperature stirring and refluxing, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material;
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating; Described PEI-QPEI/SiO
2The mass ratio of nano material, copper sulphate, water is: 1:1:8.
The reaction equation of steps A ~ E is with embodiment 1;
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 70:10:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 30 ℃ of reaction 10 h leave standstill centrifugation after a period of time, 90 ℃ of dry 6h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.03 g/g.
Claims (6)
1. nano combined timber preservative, its structural representation formula is:
In the formula:
Be nanometer SiO
2,
Be PEI,
Be QPEI,
Be Cu
2+
2. the preparation method of a nano combined timber preservative may further comprise the steps:
The surface modification of A, silica nano material: silica nano material is dispersed in the alcohol, measure an amount of γ-chloropropyl triethoxysilane, add in the reaction vessel, stir, be heated to more than the pure boiling point, constant temperature back flow reaction 8 ~ 12 h make chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with alcohol, the product after the washing is dry to be processed, and obtains the silica nano material of chloropropylation, i.e. CP/SiO
2Nano material;
The silica nano material grafting polyethylene imine of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add an amount of PEI, mixed liquor is heated, back flow reaction, reaction finishes rear to the reactant liquor centrifugation, and washing sample, remove residual PEI, obtain PEI/SiO after the drying
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, stirs to be warming up to more than the expoxy propane boiling point after lower ice bath reacts 6 ~ 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, under 50 ~ 70 ℃, carry out back flow reaction 18 ~ 24 h, after reaction finishes, filter, with alcohol washing product, drying namely gets QPEI/SiO
2Material;
D, PEI-QPEI/SiO
2Synthesizing of nano material: with QPEI/SiO
2Nano material is dispersed in the alcohol, adds an amount of γ-chloropropyl triethoxysilane, is heated to more than the pure boiling point constant temperature stirring and refluxing reaction 8 ~ 12 h, centrifugation, drying; Intermediate product after the drying is dispersed in the PEI aqueous solution, at 90 ~ 100 ℃ of lower constant temperature stirring and refluxing reaction 12 ~ 24 h, PEI is grafted on QPEI/SiO
2Nano-material surface makes PEI-QPEI/SiO
2Nano material;
E, chelated copper ion are with the PEI-QPEI/SiO that has made
2Nano material is distributed in the copper sulfate solution, and is after stirring a period of time, dry after separating.
3. preparation method as claimed in claim 2 is characterized in that:
The mass ratio of silica nano material described in the steps A, γ-chloropropyl triethoxysilane, alcohol is: 1:(0.5 ~ 1): (6 ~ 8), described silica nano material granularity is 90 ~ 150 nm, described freeze-day with constant temperature temperature is 100 ~ 150 ℃, and be 12 ~ 24 h drying time;
The condition of back flow reaction described in the step B is: 90 ~ 100 ℃ of back flow reaction 10 ~ 12 h, and the silica nano material of described surface modification, the PEI concentration in mixed liquor is respectively: 0.1 ~ 0.15 g/g and 0.2 ~ 0.3 g/g; Baking temperature is 60 ~ 100 ℃, and be 8 ~ 12 h drying time;
PEI/SiO described in the step C
2The mass ratio of nano material and expoxy propane is 1:(4 ~ 6), the PEI/SiO of described alcohol, tertiary amine
2,, the mass ratio of benzyl chloride is (2 ~ 3): 1:(1 ~ 2); Described drying condition is more than 60 ~ 100 ℃ of lower dry 24h.
QPEI/SiO described in the step D
2The mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:(6 ~ 10): (0.5 ~ 1), drying condition is: 60 ~ 100 ℃, be 12 ~ 24 h drying time; The mass ratio of described intermediate product, PEI, water is: 1:(3 ~ 5): (8 ~ 12);
PEI-QPEI/SiO described in the step e
2The mass ratio of nano material, copper sulphate, water is: 1:(0.5 ~ 1): (6 ~ 8).
4. preparation method as claimed in claim 2 is characterized in that:
Alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, the ethylene glycol among described steps A, C, the D.
5. preparation method as claimed in claim 2 is characterized in that:
Silica nano material can prepare by the following method in the described steps A:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor;
(2), add an amount of ethyl orthosilicate in the mixed liquor, 10 ~ 40 ℃ of reaction 6 ~ 10 h leave standstill centrifugation after a period of time with reactant liquor, drying makes silica nano material.
6. preparation method as claimed in claim 5 is characterized in that:
The mass ratio of alcohol, water, ammonia is (50 ~ 70) in the described step (1): (8 ~ 10): 0.5, and the concentration of ethyl orthosilicate in mixed liquor is 0.025 ~ 0.03 g/g in the step (2), drying condition is 50 ~ 90 ℃ of drying 6 ~ 10 h.
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