CN102990740B - Nano composite wood preservative and preparation method thereof - Google Patents
Nano composite wood preservative and preparation method thereof Download PDFInfo
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- CN102990740B CN102990740B CN201210342575.2A CN201210342575A CN102990740B CN 102990740 B CN102990740 B CN 102990740B CN 201210342575 A CN201210342575 A CN 201210342575A CN 102990740 B CN102990740 B CN 102990740B
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- 239000003171 wood protecting agent Substances 0.000 title claims abstract description 23
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 91
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 10
- 239000004697 Polyetherimide Substances 0.000 claims abstract 3
- 239000002086 nanomaterial Substances 0.000 claims description 137
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 57
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005119 centrifugation Methods 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000001294 propane Substances 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 12
- 229940073608 benzyl chloride Drugs 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- -1 chloropropyl Chemical group 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000013256 coordination polymer Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 abstract description 15
- 230000002335 preservative effect Effects 0.000 abstract description 13
- 150000001412 amines Chemical class 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229920001601 polyetherimide Polymers 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000002023 wood Substances 0.000 abstract 1
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 0 CC(C)(C)CCN* Chemical compound CC(C)(C)CCN* 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 244000145845 chattering Species 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 101000878581 Aplysia californica Feeding circuit activating peptides Proteins 0.000 description 1
- ZQGJEUVBUVKZKS-UHFFFAOYSA-N CC(C)(C)NC Chemical compound CC(C)(C)NC ZQGJEUVBUVKZKS-UHFFFAOYSA-N 0.000 description 1
- ISBBOOFZMFQQGC-UHFFFAOYSA-N CCN(C)C(C)(C)C(C)(C)C Chemical compound CCN(C)C(C)(C)C(C)(C)C ISBBOOFZMFQQGC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- JRQRNDCRTXFDDT-UHFFFAOYSA-N [As].C1(=CC=CC=C1)O.[Cr].[F] Chemical compound [As].C1(=CC=CC=C1)O.[Cr].[F] JRQRNDCRTXFDDT-UHFFFAOYSA-N 0.000 description 1
- CSUMZZHMIDBSGG-UHFFFAOYSA-N [B].[Cu].[Cr] Chemical compound [B].[Cu].[Cr] CSUMZZHMIDBSGG-UHFFFAOYSA-N 0.000 description 1
- OUFJROAVKKYZEN-UHFFFAOYSA-N [Cr].[Cu].[As] Chemical compound [Cr].[Cu].[As] OUFJROAVKKYZEN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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 preservative technology field, relate to a kind of nano composite wood preservative and preparation method thereof in particular.
Background technology
Wood preservative mainly comprises oil-type preservation, oil carries preservative and water ballast preservative three class, and the most widely used is at present 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.Waterborne-type preservation price is low, effective, in recent years, these preservatives are widely applied, such preservative is the main preservative of overwhelming majority material for building and home-use, but preservative easily runs off in preserving timber use procedure, and the compound such as chromium, arsenic, copper run off also can to soil, water resource and environment.
Ammonia molten alkyl cuprammonium (ACQ) is one of waterborne-type preservation that sales volume is larger in the market, and this preservative avoids chromium and arsenic violent in toxicity to the pollution of environment, but not yet solves for the problem that ammonium salt and mantoquita easily run off from timber.Along with the fast development of nanometer technology, nano anti-biotic material is the class novel antibacterial material developed in recent years.Have the timber of bibliographical information nano zine oxide process to have certain preservative efficacy, and nano material not easily run off from timber.But this material is not owing to introducing sterilizing function group, not very strong to preventing the ability of fungi erosion timber.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nano composite wood preservative and preparation method thereof, this preservative not easily runs 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 composite wood preservative, its structural representation formula is:
In formula:
for Nano-meter SiO_2
2,
for PEI,
for QPEI,
for Cu
2+
A preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: silica nano material is dispersed in alcohol, measure appropriate γ-chloropropyl triethoxysilane, add in reaction vessel, stir, be heated to more than alcohol boiling point, constant temperature back flow reaction 8 ~ 12 h, makes chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and enter washing with alcohol, the product drying process after washing, 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 DEG C, and drying time is 12 ~ 24 h;
The silica nano material grafting polyethylene imine of B, surface modification, polymine is abbreviated as PEI: be distributed in water by the silica nano material of chloropropylation, add appropriate PEI, mixed liquor is heated, back flow reaction, reaction terminates rear to reactant liquor centrifugation, and washing sample, the PEI that removing is residual, obtains PEI/SiO after drying
2nano material; Described back flow reaction condition is: 90 ~ 100 DEG C of back flow reaction 10 ~ 12 h, and silica nano material, the concentration of PEI in mixed liquor of described surface modification are respectively: 0.1 ~ 0.15 g/g and 0.2 ~ 0.3 g/g; Baking temperature is 60 ~ 100 DEG C, and drying time is 6 ~ 12 h;
C, QPEI/SiO
2the synthesis of nano material, QPEI refers to quaternised PEI: by obtained PEI/SiO
2nano material, adds appropriate expoxy propane, is warming up to more than expoxy propane boiling point, steams unreacted expoxy propane, obtain tertiary-aminated PEI/SiO after stirring lower ice bath reaction 6 ~ 10 h
2; Pour appropriate alcohol into tertiary-aminated PEI/SiO
2in, add appropriate benzyl chloride, at 50 ~ 70 DEG C, carry out back flow reaction 18 ~ 24 h, after reaction terminates, filter, use alcohol washed product, dry, obtain QPEI/SiO
2material; Described PEI/SiO
2the mass ratio of nano material and expoxy propane is 1:(4 ~ 6), described alcohol, tertiary-aminated PEI/SiO
2,, benzyl chloride mass ratio be (2 ~ 3): 1:(1 ~ 2); Described drying condition is drying more than 24 at 60 ~ 100 DEG C;
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in alcohol, adds appropriate γ-chloropropyl triethoxysilane, is heated to more than alcohol boiling point, constant temperature stirring and refluxing reaction 8 ~ 12 h, and centrifugation is dry; Be dispersed in by intermediate product after drying in the PEI aqueous solution, at 80 ~ 100 DEG C, constant temperature stirring and refluxing reaction 12 ~ 24h, is grafted on QPEI/SiO by PEI
2nano-material surface, obtained 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 DEG C, and drying time is 12 ~ 24 h; The mass ratio of described intermediate product, PEI, water is: 1:(3 ~ 5): (8 ~ 12);
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated; Described PEI-QPEI/SiO
2the mass ratio of nano material, copper sulphate, water is: 1:(0.5 ~ 1): (6 ~ 8).
Several organic molecules that in above reaction equation, single nanometer silicon dioxide particle can react with participation, some polymer chains react.
In described steps A, C, D, alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol.
In described steps A, silica nano material can be prepared by the following method:
(1), get appropriate alcohol, water, ammoniacal liquor mixes, obtained mixed liquor;
(2), in mixed liquor, add appropriate ethyl orthosilicate (TEOS), 10 ~ 40 DEG C of reaction 6 ~ 10 h, leave standstill centrifugation after a period of time by reactant liquor, dry, obtained silica nano material.
Alcohol, water, ammonia (NH in 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 ~ 0.03g/g in step (2), and drying condition is 50 ~ 90 DEG C 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 there is stable performance, avirulence, nonirritant and use safety and high-quality immobilization wood preservative, enhanced the preservative efficacy of this material at nano-material surface Relatively centralized by functional group, be mixed with traditional wood preservative heavy metal ion or small molecule quaternary ammonium salt and mantoquita and form ratio, and product of the present invention utilizes functional silica nano material and chelated copper ion is prepared from, solidification avoids the shortcoming that traditional preservatives is easy to run off from timber, and functional group also enhances the preservative efficacy of this material at nano-material surface Relatively centralized, nano composite wood preservative of the present invention not easily runs off from timber, and there is higher biocidal efficacies, the environmental pollution that a large amount of losses reducing preservative cause.
Accompanying drawing illustrates:
Fig. 1 is the infrared spectrum of nanostructure intermediate prepared by the embodiment of the present invention 1.
In 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.
Embodiment
Embodiment 1
A kind of nano composite wood preservative, its structural representation formula is:
In formula:
for Nano-meter SiO_2
2,
for PEI,
for QPEI,
for Cu
2+
A preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: be that the silica of 100 nm is dispersed in methyl alcohol by granularity, measure appropriate γ-chloropropyl triethoxysilane, add in there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating, at 66 DEG C of constant temperature back flow reaction 8 h, makes chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and enter washing with methyl alcohol, 100 DEG C of drying 12 h of the product constant temperature after 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 water, add PEI, wherein the silica nano material of surface modification, the concentration of PEI in mixed liquor are respectively: 0.1 g/g and 0.2 g/g, mixed liquor is heated, back flow reaction 10 h at 90 DEG C, reaction terminates rear to reactant liquor centrifugation, and uses methanol wash sample, the PEI that removing is residual, obtains PEI/SiO after 60 DEG C of drying 6 h
2nano material;
The reaction equation of step B is as follows:
C, QPEI/SiO
2the synthesis of nano material: by obtained PEI/SiO
2nano material, adds appropriate expoxy propane, wherein PEI/SiO
2the mass ratio of nano material and expoxy propane is 1:4, stirs after lower ice bath reacts 6 h and is warming up to 35 DEG C, steam unreacted expoxy propane, obtain tertiary-aminated PEI/SiO
2; Pour proper amount of methanol into tertiary-aminated PEI/SiO
2in, add appropriate benzyl chloride, wherein methyl alcohol, tertiary-aminated PEI/SiO
2,, benzyl chloride mass ratio be 2:1:1; At 50 DEG C, carry out back flow reaction 18 h, after reaction terminates, filter, use methanol wash product, at 80 DEG C, dry 24 h, obtain QPEI/SiO
2material;
The reaction equation of step C is as follows:
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in methyl alcohol, adds appropriate 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 DEG C, and stirring and refluxing reacts 8 h, centrifugation, 100 DEG C of drying 12 h; Be dispersed in by intermediate product after drying in the PEI aqueous solution, wherein the mass ratio of intermediate product, PEI, water is: 1:3:8; At 90 DEG C, constant temperature stirring and refluxing reacts 12 h, and PEI is grafted on QPEI/SiO
2nano-material surface, obtained PEI-QPEI/SiO
2nano material;
The reaction equation of step D is as follows:
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated; 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 nanostructure intermediate prepared by embodiment 1 is shown in Fig. 1, and see from figure, each intermediate is at 1083 cm
-1there is an extremely strong wide absworption peak at 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 to the silicone hydroxyl and adsorbed water that form hydrogen bond, and after chemical modification, this peak weakens to some extent, and at 2953 cm
-1there is C-H key chattering absworption peak in place, shows Nano-meter SiO_2
2surface realizes chloropropylation, strengthens gradually by 2-5 by can be observed C-H key chattering absworption peak in figure, this is because intermediate C-H key in grafting PEI and quaternization process increases gradually.Chloropropylation SiO
2after reacting with PEI in figure 3,4,5 at 1460 cm
-1there is C-N key stretching vibration absworption peak in place, shows that PEI is successfully grafted to Nano-meter SiO_2
2surface.By 4,5 observing after sample is quaternized at 1627,1417,696,758 cm in figure
-1there is phenyl ring characteristic absorption peak, show that the PE I be grafted on silica gel there occurs quaterisation, defines functional material QPEI/SiO
2.Quaternary ammonium salt does not have INFRARED ABSORPTION, does not therefore occur corresponding absworption peak in 4,5 in the drawings.By 5 observing after sample again grafting PEI at 1460 cm in figure
-1c-N key stretching vibration absworption peak that place occurs comparatively strengthens in 4 in figure, and this shows that PEI is successfully grafted to QPEI/SiO again
2nano-material surface.
Embodiment 2
A kind of nano composite wood preservative, its structural representation formula is with embodiment 1;
A preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: by granularity be 120nm silica dispersion in ethanol, measure appropriate γ-chloropropyl triethoxysilane, add in there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating, at 80 DEG C of constant temperature back flow reaction 10 h, makes chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and enter washing with methyl alcohol, 120 DEG C of drying 15 h of the product constant temperature after 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 water, add PEI, wherein the silica nano material of surface modification, the concentration of PEI in mixed liquor are respectively: 0.12 g/g and 0.25 g/g, mixed liquor is heated, back flow reaction 12 h at 90 DEG C, reaction terminates rear to reactant liquor centrifugation, and uses ethanol washing sample, the PEI that removing is residual, obtains PEI/SiO after 80 DEG C of drying 10 h
2nano material;
C, QPEI/SiO
2the synthesis of nano material: by obtained PEI/SiO
2nano material, adds appropriate expoxy propane, wherein PEI/SiO
2the mass ratio of nano material and expoxy propane is 1:5, stirs after lower ice bath reacts 8 h and is warming up to 35 DEG C, steam unreacted expoxy propane, obtain tertiary-aminated PEI/SiO
2; Pour ethanol in proper amount into tertiary-aminated PEI/SiO
2in, add appropriate benzyl chloride, wherein ethanol, tertiary-aminated PEI/SiO
2,, benzyl chloride mass ratio be 2.5:1:1.5; At 60 DEG C, carry out back flow reaction 20 h, after reaction terminates, filter, use ethanol washed product, at 80 DEG C, dry 28 h, obtain QPEI/SiO
2material;
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in ethanol, adds appropriate 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 DEG C, and stirring and refluxing reacts 10 h, centrifugation, 80 DEG C of drying 10 h; Be dispersed in by intermediate product after drying in the PEI aqueous solution, wherein the mass ratio of intermediate product, PEI, water is: 1:4:10; At 90 DEG C, constant temperature stirring and refluxing reacts 15 h, and PEI is grafted on QPEI/SiO
2nano-material surface, obtained PEI-QPEI/SiO
2nano material;
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated; 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 is prepared by following steps:
(1), get appropriate alcohol, water, ammoniacal liquor mixes, obtained mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 50:8:0.5;
(2), in mixed liquor, appropriate ethyl orthosilicate (TEOS) is added, 10 DEG C of reaction 10h, leave standstill centrifugation after a period of time, 50 DEG C of drying 10 h by reactant liquor, obtained silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.025 g/g.
Embodiment 3
A kind of nano composite wood preservative, its structural representation formula is with embodiment 1;
A preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: be that the silica of 150nm is dispersed in propyl alcohol by granularity, measure appropriate γ-chloropropyl triethoxysilane, add in there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating, at 88 DEG C of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and enter washing with propyl alcohol, 150 DEG C of drying 18 h of the product constant temperature after 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 water, add PEI, wherein the silica nano material of surface modification, the concentration of PEI in mixed liquor are respectively: 0.15 g/g and 0.3 g/g, mixed liquor is heated, back flow reaction 10 h at 100 DEG C, reaction terminates rear to reactant liquor centrifugation, and uses propanol rinse sample, the PEI that removing is residual, obtains PEI/SiO after 100 DEG C of drying 10 h
2nano material;
C, QPEI/SiO
2the synthesis of nano material: by obtained PEI/SiO
2nano material, adds appropriate expoxy propane, wherein PEI/SiO
2the mass ratio of nano material and expoxy propane is 1:6, stirs after lower ice bath reacts 10 h and is warming up to 35 DEG C, steam unreacted expoxy propane, obtain tertiary-aminated PEI/SiO
2; Pour appropriate propyl alcohol into tertiary-aminated PEI/SiO
2in, add appropriate benzyl chloride, wherein propyl alcohol, tertiary-aminated PEI/SiO
2,, benzyl chloride mass ratio be 3:1:2; At 70 DEG C, carry out back flow reaction 24 h, after reaction terminates, filter, use propanol rinse product, at 100 DEG C, dry 24 h, obtain QPEI/SiO
2material;
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in propyl alcohol, adds appropriate γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2the mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:10:1, is heated to 88 DEG C, and stirring and refluxing reacts 12 h, centrifugation, 100 DEG C of drying 18 h; Be dispersed in by intermediate product after drying in the PEI aqueous solution, wherein the mass ratio of intermediate product, PEI, water is: 1:5:12; At 100 DEG C, constant temperature stirring and refluxing reaction 12h, is grafted on QPEI/SiO by PEI
2nano-material surface, obtained PEI-QPEI/SiO
2nano material;
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated; 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 is prepared by following steps:
(1), get appropriate alcohol, water, ammoniacal liquor mixes, obtained mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 60:9:0.5;
(2), in mixed liquor, appropriate ethyl orthosilicate (TEOS) is added, 40 DEG C of reaction 6h, leave standstill centrifugation after a period of time, 80 DEG C of drying 8 h by reactant liquor, obtained silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.028 g/g.
Embodiment 4
A kind of nano composite wood preservative, its structural representation formula is with embodiment 1;
A preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: be that the silica of 110 nm is dispersed in ethylene glycol by granularity, measure appropriate γ-chloropropyl triethoxysilane, add in there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating, at 198 DEG C of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and spent glycol enters washing, 150 DEG C of drying 24 h of the product constant temperature after 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 water, add PEI, wherein the silica nano material of surface modification, the concentration of PEI in mixed liquor are respectively: 0.12 g/g and 0.3 g/g, mixed liquor is heated, back flow reaction 12 h at 100 DEG C, reaction terminates rear to reactant liquor centrifugation, and spent glycol washing sample, the PEI that removing is residual, obtains PEI/SiO after 100 DEG C of drying 12 h
2nano material;
C, QPEI/SiO
2the synthesis of nano material: by obtained PEI/SiO
2nano material, adds appropriate expoxy propane, wherein PEI/SiO
2the mass ratio of nano material and expoxy propane is 1:6, stirs after lower ice bath reacts 10 h and is warming up to 36 DEG C, steam unreacted expoxy propane, obtain tertiary-aminated PEI/SiO
2; Pour proper amount of glycol into tertiary-aminated PEI/SiO
2in, add appropriate benzyl chloride, wherein propyl alcohol, tertiary-aminated PEI/SiO
2,, benzyl chloride mass ratio be 3:1:2; At 70 DEG C, carry out back flow reaction 24 h, after reaction terminates, filter, spent glycol washed product, at 60 DEG C, dry 30 h, obtain QPEI/SiO
2material;
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in ethylene glycol, adds appropriate γ-chloropropyl triethoxysilane, wherein QPEI/SiO
2the mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:10:1, is heated to 198 DEG C, and stirring and refluxing reacts 12 h, centrifugation, 60 DEG C of drying 24 h; Be dispersed in by intermediate product after drying in the PEI aqueous solution, wherein the mass ratio of intermediate product, PEI, water is: 1:5:12; At 80 DEG C, constant temperature stirring and refluxing reacts 24 h, and PEI is grafted on QPEI/SiO
2nano-material surface, obtained PEI-QPEI/SiO
2nano material;
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated; 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 is prepared by following steps:
(1), get appropriate alcohol, water, ammoniacal liquor mixes, obtained mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 70:10:0.5;
(2), in mixed liquor, appropriate ethyl orthosilicate (TEOS) is added, 30 DEG C of reaction 10h, leave standstill centrifugation after a period of time, 90 DEG C of dry 6h by reactant liquor, obtained silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.03 g/g.
Claims (3)
1. a preparation method for nano composite wood preservative, comprises the following steps:
The surface modification of A, silica nano material: be dispersed in by silica nano material in alcohol, measures γ-chloropropyl triethoxysilane, adds in reaction vessel, stir, be heated to more than alcohol boiling point, constant temperature back flow reaction 8 ~ 12h, make chloropropyl be coupling in silica nano material surface; After having reacted, centrifugation, and wash with alcohol, the product drying process after washing, 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 water, add PEI, mixed liquor is heated, back flow reaction, reaction terminates rear to reactant liquor centrifugation, and washing sample, the PEI that removing is residual, obtains PEI/SiO after drying
2nano material;
C, QPEI/SiO
2the synthesis of nano material: by obtained PEI/SiO
2nano material, adds expoxy propane, is warming up to more than expoxy propane boiling point, steams unreacted expoxy propane, obtain tertiary-aminated PEI/SiO after stirring lower ice bath reaction 6 ~ 10h
2; Pour alcohol into tertiary-aminated PEI/SiO
2in, add benzyl chloride, at 50 ~ 70 DEG C, carry out back flow reaction 18 ~ 24h, after reaction terminates, filter, use alcohol washed product, dry, obtain QPEI/SiO
2material;
D, PEI-QPEI/SiO
2the synthesis of nano material: by QPEI/SiO
2nano material is dispersed in alcohol, adds γ-chloropropyl triethoxysilane, is heated to more than alcohol boiling point, constant temperature stirring and refluxing reaction 8 ~ 12h, and centrifugation is dry; Be dispersed in by intermediate product after drying in the PEI aqueous solution, at 90 ~ 100 DEG C, constant temperature stirring and refluxing reaction 12 ~ 24h, is grafted on QPEI/SiO by PEI
2nano-material surface, obtained PEI-QPEI/SiO
2nano material;
E, chelated copper ion, by obtained PEI-QPEI/SiO
2nano material is distributed in copper sulfate solution, after stirring a period of time, dry after being separated;
In described steps A, C, D, alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol;
The mass ratio of silica nano material described in steps A, γ-chloropropyl triethoxysilane, alcohol is: 1:(0.5 ~ 1): (6 ~ 8), described silica nano material granularity is 90 ~ 150nm, described baking temperature is 100 ~ 150 DEG C, and drying time is 12 ~ 24h;
The condition of back flow reaction described in step B is: 90 ~ 100 DEG C of back flow reaction 10 ~ 12h, and silica nano material, the concentration of PEI in mixed liquor of described surface modification are respectively: 0.1 ~ 0.15g/g and 0.2 ~ 0.3g/g; Baking temperature is 60 ~ 100 DEG C, and drying time is 8 ~ 12h;
PEI/SiO described in step C
2the mass ratio of nano material and expoxy propane is 1:(4 ~ 6), described alcohol, tertiary-aminated PEI/SiO
2, benzyl chloride mass ratio be (2 ~ 3): 1:(1 ~ 2); Described drying condition is dry more than 24h at 60 ~ 100 DEG C;
QPEI/SiO described in step D
2the mass ratio of nano material, alcohol, γ-chloropropyl triethoxysilane is 1:(6 ~ 10): (0.5 ~ 1), drying condition is: 60 ~ 100 DEG C, and drying time is 12 ~ 24h; The mass ratio of described intermediate product, PEI, water is: 1:(3 ~ 5): (8 ~ 12);
PEI-QPEI/SiO described in step e
2the mass ratio of nano material, copper sulphate, water is: 1:(0.5 ~ 1): (6 ~ 8).
2. preparation method as claimed in claim 1, is characterized in that:
In described steps A, silica nano material can be prepared by the following method:
(1), get alcohol, water, ammoniacal liquor mixes, obtained mixed liquor;
(2), in mixed liquor add ethyl orthosilicate, 10 ~ 40 DEG C of reaction 6 ~ 10h, leave standstill centrifugation after a period of time by reactant liquor, dry, obtained silica nano material;
In described step (1), the mass ratio of alcohol, water, ammonia is (50 ~ 70): (8 ~ 10): 0.5, in step (2), the concentration of ethyl orthosilicate in mixed liquor is 0.025 ~ 0.03g/g, and drying condition is 50 ~ 90 DEG C of drying 6 ~ 10h.
3. a nano composite wood preservative, uses preparation method's preparation of claim 1 or 2.
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| CN104045857B (en) * | 2014-06-16 | 2016-04-13 | 安徽师范大学 | A kind of silicon-dioxide Chitosan Composites, preparation method and application thereof |
| CN104526806B (en) * | 2014-12-05 | 2016-09-28 | 中南林业科技大学 | The preparation method of bamboo wood mould preservative |
| CN108350170A (en) * | 2015-11-04 | 2018-07-31 | 新加坡科技研究局 | By the functionalized antibacterium particle for water sterilization of substituted polyalkyleneimines and its derivative |
| CN108608543A (en) * | 2018-04-24 | 2018-10-02 | 阜南县宇翔工艺品有限公司 | A kind of wicker products novel mildew resistant method |
| CN108748509A (en) * | 2018-05-17 | 2018-11-06 | 阜南县宇翔工艺品有限公司 | A method of promoting bamboo furniture L-type corner hardware Joint Properties |
| CN109593210B (en) * | 2018-12-13 | 2021-07-06 | 青岛理工大学 | Antifouling bacteriostatic sand and preparation method thereof |
| CN110076869A (en) * | 2019-06-13 | 2019-08-02 | 毛克升 | A kind of bamboo wood anti-mould and anti-moth inorganic agent and preparation method thereof and construction technology |
| CN110387046A (en) * | 2019-07-30 | 2019-10-29 | 南通职业大学 | A kind of alkylated polyethyleneimine grafting SiOxThe preparation method of nano antibacterial agent |
| CN113800816B (en) * | 2020-06-12 | 2022-10-21 | 深圳先进电子材料国际创新研究院 | Epoxy plastic packaging material and preparation method and application thereof |
| CN112126153B (en) * | 2020-09-09 | 2022-10-14 | 武汉金发科技有限公司 | Polypropylene composite material and preparation method thereof |
| CN112796160A (en) * | 2021-02-05 | 2021-05-14 | 上海万戈工贸发展有限公司 | Preparation method of chelated copper ion polymer and antibacterial barrier composite paper/paperboard thereof |
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