CN1268678C - Preparation method of chitin metal salt wood preservative and its application - Google Patents
Preparation method of chitin metal salt wood preservative and its application Download PDFInfo
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- CN1268678C CN1268678C CN 02120352 CN02120352A CN1268678C CN 1268678 C CN1268678 C CN 1268678C CN 02120352 CN02120352 CN 02120352 CN 02120352 A CN02120352 A CN 02120352A CN 1268678 C CN1268678 C CN 1268678C
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Abstract
The present invention relates to a preparation method for a chitosan metal salt used as a wood preservative. At least one kind of chitosan or a chitosan derivative is dispersed in water; then, at least one metal salt selected from copper, zinc or rare earth is dispersed into dispersing liquid of the chitosan or the chitosan derivative, wherein the proportion of the chitosan to the metal salt is 1:0.3 to 2.5(W/W); the dispersing liquid is heated for 1.5 to 5 hours at the temperature of 35 to 60DEG C so as to make the metal salt and the chitosan or the chitosan derivative form a water insoluble chelate complex of the chitosan and the metal salt; then, at least one kind of dilute acid is added into the chelate complex to solubilize the chitosan and the metal salt so as to form a water soluble substance of which the pH value is regulated to 2 to 6.
Description
Technical field
The present invention relates to the preparation method of the sanitas that a kind of wood protection and wood preservation use, specifically, relate to a kind of preparation method of chitin metal salt wood preservative.
The invention still further relates to the application of foregoing preservatives in wood preservative.
Background technology
Timber is natural biologic material, also is a kind of renewable resources, is the important raw and processed materials of human survival and development, and is closely bound up with the human lives.But it has tangible biological characteristics, thereby endangered by biologies such as wood-decay fungi, insect, marine borer and microorganism, thereby cause Wood Discoloration, rotten and damage by worms, had a strong impact on the work-ing life of timber, increased the consumption of timber, the forest reserves that waste reduces have day by day also limited Application Areas wooden, bamboo wood.According to statistics, the U.S. is lost up to 5,000,000,000 dollars by the timber that wood-decay fungi and insect are caused every year.For making timber avoid these harm, give full play to its use value, prolong normal timber life, just must carry out anticorrosion mildew-resistant and handle wood, bamboo wood, make it durable, thus the amount of demaning reduction, the forest reserves that protection is human.
Wood, bamboo wood sanitas kind is a lot, roughly can divide oily class (creosote), oil soluble and waterborne-type preservation.Oil class and oil-solvent preservative are handled timber, though the sanitas resistance leachability is good, and wood, bamboo wood color change after the former handles, and smell is unhappy, and the oil spilling phenomenon easily takes place, and the processing material glues together and the paint effect is bad.The latter is then owing to adopt expensive organic reagent, the processing cost height, and must possess higher fire resistance.Waterborne-type preservation is because cheap, and it is clean to handle the back face, has no irritating odor, and is good to timber paint and glue performance, do not increase advantage such as combustibility and is widely used.Though most of waterborne-type preservation favorable anti-corrosion effect, resistance leachability is poor.Thereby some toxic substances are released in the environment, cause environmental pollutions such as soil and underground water.
Along with cry one wave of global Sustainable development, bio-diversity conservation and environment protection action exceeds a wave; people more and more pay close attention to the environmental pollution and the toxicity problem of the pharmaceutical chemicals of wood preservation field existence; as creosote, copper chromium arsenic salt (CCA), acidic chromium mantoquita (ACC), cuprammonium arsenic salt (ACA) though etc. can protect timber effectively; but they are very big to HUMAN HEALTH and environmental hazard; arsenic salt and chromic salts are human carcinogen's materials, and creosote, Pentachlorophenol and its esters, lindane etc. also can have carcinogenesis to human body.Moreover, these after the timber after the rotproofing is discarded processing and utilize again and also have a lot of problems, also to environment generation secondary pollution.As CCA is a kind ofly to generally acknowledge that in the world effect is preferable, use sanitas more widely, but resistance leachability is relatively poor, and the arsenic that comes out of running off is very harmful to human health and environment, and the U.S. and European Union have forbidden in the recent period and limited its use.Therefore, people expect to research and develop feature of environmental protection wood protection and handle medicament, develop human body and all safe sanitas of environment, substitute traditional wood preservative.
Summary of the invention
The object of the present invention is to provide a kind of chitin metal salt wood preservative, it contains at least a chitosan or chitosan derivatives, at least a by being selected from the metallic salt of cupric, zinc and rare earth, at least a diluted acid and water make the chitin metal salt solubilising form water-soluble substances.
Be applicable to that wood preservative chitin metal salt of the present invention is easy to form by the metallic salt reacting by heating that is selected from chitosan or chitosan derivatives and is selected from cupric, zinc and rare earth.
Wood preservative provided by the invention can prepare with following method: at least a chitosan of adding or chitosan derivatives are dispersed in the water in water, in 35-60 ℃ of water-bath under the heated and stirred, add at least a copper, the zinc of being selected from or/and the metallic salt of rare earth makes it dissolving, wherein the ratio of chitosan and metallic salt is 1: 0.3-2.5 (W/W), stir after 1.5-5 hour and take out, centrifugation, abandon supernatant liquor, it is colourless to be washed with distilled water to supernatant liquor, dry under 55-75 ℃, gets meal; In powder, add diluted acid, stir and make it dissolving, and adjusting pH value is 2-6.
Described chitosan or chitosan derivatives comprise chitosan, water-soluble chitosan, cm-chitosan, N-acetylated chitosan sugar, N-propionyl chitosan, N-Butyrylation chitosan, N-hexanoyl chitosan, the adjacent benzyl chitosan of N-and/or N-carboxyl chitosan;
The metallic salt of described cupric, zinc comprises vitriol, phosphoric acid salt, hydrochloride or the nitrate of cupric and/or zinc.
Described rare earth metal salt is rare earth chloride, rare-earth phosphorate and/or rare earth nitrate.
Described diluted acid is hydrochloric acid, nitric acid, formic acid, acetate, citric acid, Mono Chloro Acetic Acid, pyruvic acid, lactic acid or phenylformic acid.
The concentration of described chitin metal salt is 0.1-20%.
The application of wood preservative of the present invention is that sanitas is coated to wood surface to be processed; In the pressurization coating equipment that is fit to, by the sanitas former state or further be diluted in the water or after in organic solvent and the water, be added in the timber with the method for soaking or flood.
Sanitas provided by the invention has fabulous chemical stability, the resistance leachability energy is good, preservative effect is high and the wood preservative of low toxicity, can prevent the generation of foxy or eliminate foxy.
Wood preservative provided by the invention, compare with internationally famous wood preservative CCA, its preservative effect and CCA are approaching, but wood preservative of the present invention in timber the fixation rate height, resistance leachability is strong, toxicity is little, and itself do not have the loss of heavy metal elements such as arsenic and cause environmental pollution soil and underground water etc.
Embodiment
Embodiment and application Comparative Examples by narrating below have further understanding to the present invention.
Embodiment 1: the preparation of chitin metal salt sanitas (is example with the chitosan mantoquita)
In 1500ml distilled water, add CuCl
275g makes it dissolving, heats in 40-50 ℃ of water-bath, adds 75 gram chitosans while stirring.Constant speed is taken out after stirring (stirring velocity: 300-400 rev/min) 2h, and supernatant liquor is abandoned in centrifugation, and it is colourless to be washed with distilled water to supernatant liquor, is dried to constant weight under 60 ± 2 ℃, obtains chitosan-metal mantoquita powder-product.
Take by weighing an amount of chitin metal salt, add 1% acetic acid aqueous solution, and constantly stirring makes it dissolving, being mixed with needs the chitosan-metal of concentration salts solution.
Embodiment 2: anti-white rot experiment
According to China's standard " wood preservative is to rot fungi toxicity test chamber test method " (LY/T1283-1998), measure the anti-white rot effect of timber of chitin metal salt.
The preparation of A, sample
Intercepting Cortex Populi Tomentosae (Populus tomentosa Carr.) healthy sapwood, saw is separated into 20mm * 20mm * 10mm (thickness * width * rift grain direction) small sample, with fine sandpaper with its surface grinding.Sample wooden unit elder generation dries by the fire 2h down at 60 ℃, dries by the fire 2h down at 80 ℃ again, dries to constant weight under 105 ± 2 ℃ then, uses scales/electronic balance weighing, gets the heavy T of test block over dry
1Test block with similar weight is placed on same group (weight difference is not more than 0.5g between the test block), 6 every group then.
B, bacterial classification and cultivation thereof
Select Corilus versicolor Quel. (Coriolous versicolor) as anti-white rot experimental strain.
Adopt maltose nutrient agar and river sand sawdust substratum to be used for cultivating and the inoculation whiterot fungi, wherein the maltose nutrient agar is used for inoculation.
(1) the maltose nutrient agar is got homemade maltose solution adding distilled water, being diluted to ripple Mei Shi proportion is 1.03, measure 500ml, pour in the 1000ml beaker, add agar 8.75g, place on the electric furnace and heat, after treating that agar dissolves, while hot this solution is poured in three 250ml Erlenmeyer flasks, the bottle plug tampon also wraps waterproof paper, place vapor sterilization pot (0.1MPa, 121 ℃) sterilization 20min, standby.
(2) river sand sawdust substratum with the red pool, Semen Maydis powder, timber sapwood sawdust (20-30 order), clean dry river sand (20-30 order) in 1: 8.5: 15: 150 (mass ratio) ratio is mixed thoroughly, pour 500ml Erlenmeyer flask (adding 180 this kind of gram mixtures in each Erlenmeyer flask) into, putting into specification on the surface after the leveling respectively is 3 of 22mm * 22mm * 3mm (thickness * width * rift grain direction) feed wood chips, 3 feed wood chips are placed apart separately, and shape triangular in shape.In bottle, add incoming wave Mei Shi proportion slowly and be 1.03 100ml maltose solution.Seal with sealing film then, sterilization 1h takes out in vapor sterilization pot (0.1MPa, 121 ℃), places Bechtop, the inoculation of cooling back.
The preparation of C, chitin metal salt antiseptic solution
Take by weighing an amount of chitin metal salt, add 1% acetic acid aqueous solution, and constantly stirring makes it dissolving.The chitosan mantoquita antiseptic solution of preparation is totally 5 concentration (seeing Table 1).
Fill a prescription in the CCA standard that provides according to ASTM, select the low A type CCA of arsenic content in contrast, cofabrication CCA (copper chromium arsenic) antiseptic solution is used K
2CrO
7, CuSO
45H
2O and Na
3AsO
47H
2O is a reagent, and compound concentration is 0.75%, 1.50% and 3.00% CCA solution, and handles wood sample, and the corrosion resistant performance of handling sample with chitin metal salt contrasts.
D, sample impregnate processing
(1) sample is prepared to get Cortex Populi Tomentosae sapwood sample, and with its surface grinding, elder generation dries by the fire 2h down at 60 ℃ with fine sandpaper, and baking 2h under 80 ℃ dries to constant weight under 105 ± 2 ℃ then again, uses scales/electronic balance weighing, gets the heavy T of test block over dry
1Test block with similar weight is placed on same group (weight difference is not more than 0.5g between the test block) then, and 6 every group, make marks with water resistant ink, be stored in the moisture eliminator standby.
(2) dip treating of test block is put into same beaker with 6 samples of each concentration of treatment, keeps a fixed gap between sample, presses lastblock glass weight above, puts into vacuum drier, vacuumizes 2h under 0.1kPa pressure.Open the vacuum drier piston then at leisure, under vacuum state, antiseptic solution, the usefulness distilled water (contrast) for preparing is sucked in the beaker, when the sanitas soakage exceeds the 2-3cm left and right sides, wooden unit plane, stop liquid feeding, dip treating 4h under normal pressure.Takes out test block, wipe the surface anticorrosion agent solution gently, and the sub-balance of electricity consumption immediately weighs, the weight T of test block after impregnating
2
Test block after weighing is earlier air-dry, dries by the fire to over dry again, weighs, and must flood the heavy T of back test block over dry
3Test block is stored in the moisture eliminator standby.By formula (1) calculates metal ion maintenance dose in the sanitas.
Formula (1): W
1=(T
2-T
1) * C
1* 1000/V
In the formula: W
1-metal ion maintenance dose, unit: kg/m
3
T
2Back weight in wet base, unit: g are handled in-test block
T
1Over dry was heavy before-test block was handled, unit: g
C
1Metal ion weight percent (%) in-antiseptic solution
V-handles the volume of test block, and unit is cm
3
(3) sanitas leaching test
The processing test block of the same maintenance dose of a kind of sanitas is placed in the suitable beaker, on press the inertia weight, press the 50ml/ piece and add distilled water.Beaker is placed in the vacuum drier, under 0.1kPa pressure, vacuumize 1.5h.Recover normal pressure, change water (50ml/ piece), continue 14d every 24h.Take out test block, dry by the fire to over dry after air-dry, weigh, the heavy T of back test block over dry must run off
4With aforesaid method distilled water is handled test block (contrast) and also carry out leaching test.
By formula (2) and (3) distinguish computing test block metal ion number of dropouts and fixation rate.
Formula (2): W
2=(T
3-T
4-W
0) * C
2* 1000/V
In the formula: W
2-metal ion number of dropouts, unit: kg/m
3
T
3Over dry heavy (being that test block over dry after impregnation is heavy) before-test block is run off, unit: g
T
4The over dry of-test block after running off is heavy, unit: g
W
0Over dry was heavy after over dry heavily deducted and runs off before-reference block ran off and handles, with this number of dropouts as the contained cold water extract of test block itself, unit: g
C
2Metal content in the-sanitas (%)
V-handles the volume of test block, and unit is cm
3
Formula (3): PL%=(W
1-W
2)/W
1* 100 (2)
In the formula: PL-metal ion fixation rate, represent with percentage ratio
W
1-genus ion maintenance dose, unit: kg/m
3
W
2-metal ion number of dropouts, unit: kg/m
3
The sterilization of E, sample and inoculation
Corilus versicolor Quel. is inoculated on the maltose nutrient agar, and cultivation 5-9d (temperature: 27 ± 2 ℃, relative humidity: 70 ± 5%), stand-by.
Get the clean Erlenmeyer flask of 250ml several, put one and the sizable filter paper in the bottle end in each bottle, add 5ml distilled water respectively, then same group of test block put into, seal with sealing film, and mark, place the vapor sterilization pot 20min (0.1Mpa that sterilizes with water resistant ink, 121 ℃), carry out the sample sterilization.
To on above-mentioned maltose nutrient agar, cultivate the whiterot fungi colony edge of 5-9d, buy the bacterium cake that cut-off directly is 1cm respectively, be inoculated into three feed wood chip central authorities in the 500ml Erlenmeyer flask that river sand sawdust substratum is housed, seal with punch tool.
F, the rotten experiment of sample
The culturing bottle that fills sample is positioned in the culturing room cultivates, keep 28 ± 2 ℃ of temperature, relative humidity 70 ± 5% is covered by mycelia fully up to the feed wood chip.Test block after will sterilizing then is placed on the interior feed wood chip of Erlenmeyer flask (cross section of test block contacts with the feed wood chip that is covered by mycelia), continues to cultivate in culturing room (humiture is the same).After three months, take out test block, carefully scrape off the mycelia and the impurity on surface, dry by the fire to over dry after air-dry, weigh, the heavy T of rotten back over dry
5By formula (4) calculate rotten back rate of weight loss.
Formula (4): weightless %=(T
4-T
5)/T
4* 100
In the formula: T
4-rotten preceding sample over dry is heavy, and the back over dry that promptly runs off is heavy, unit: g
T
5-rotten back sample over dry is heavy, unit: g
G, sanitas preservative effect
The anti-white rot experimental result of chitosan mantoquita (CCS) timber is as shown in table 1.Compare with CCA, the metal ion fixation rate of chitosan mantoquita all increases, and preservative effect when the chitosan copper salt concn reaches 0.12%, just reaches corrosion resistant I level.
Anti-white rot experimental concentration of table 1 chitosan mantoquita timber and efficiency of preservation result
| The sanitas title | Concentration of preservatives (%) | Metal ion fixation rate (%) | Rotten back weightless (%) | The corrosion resistant grade |
| Do not have | 0 | 0 | 54.00 | IV |
| CCS | 0.01 | 76.84 | 32.4 | III |
| CCS | 0.12 | 85.75 | 9.70 | I |
| CCS | 0.48 | 92.85 | 4.70 | I |
| CCS | 0.96 | 94.07 | 1.14 | I |
| CCS | 2.16 | 82.25 | 0.05 | I |
| CCA | 0.75 | 78.33 | 11.72 | II |
| CCA | 1.50 | 76.55 | 3.40 | I |
| CCA | 3.00 | 78.35 | 0.13 | I |
Remarks: the corrosion resistant grade according to foxy after percentage loss of weight divide, wherein to pourous wood:
Corrosion resistant I:0-10%; Corrosion resistant level II:11-30%; Corrosion resistant III:31-50% slightly; Corrosion resistant IV not:＞50%
Embodiment 3: anti-brown rot experiment
According to China's standard " wood preservative is to rot fungi toxicity test chamber test method " (LY/T1283-1998), measure the wood preservation effect of chitin metal salt and other sanitas.
The preparation of A, sample
The healthy sapwood of intercepting Pinus massoniana Lamb (Pinus massoniana Lamb.) sapwood, saw is separated into 20mm * 20mm * 10mm (thickness * width * rift grain direction) small sample, with fine sandpaper with its surface grinding.Sample wooden unit elder generation dries by the fire 2h down at 60 ℃, dries by the fire 2h down at 80 ℃ again, dries to constant weight under 105 ± 2 ℃ then, uses scales/electronic balance weighing, gets the heavy T of test block over dry
1Test block with similar weight is placed on same group (weight difference is not more than 0.5g between the test block), 6 every group then.
B, bacterial classification and cultivation thereof
Select cotton rotten transverse hole fungus (Poria placenta) to be anti-brown rot experimental strain.
Adopt maltose nutrient agar and river sand sawdust substratum to be used for cultivating and inoculating cotton rotten transverse hole fungus, wherein the maltose nutrient agar is used for inoculation.The preparation of maltose nutrient agar and river sand sawdust substratum, cotton rotten transverse hole fungus are cultivated with embodiment two.
The preparation of C, chitosan-metal zinc salt antiseptic solution
Preparation is the chitosan zinc salt antiseptic solution (seeing Table 2) of totally 5 concentration.Take by weighing an amount of chitosan zinc salt, add 1% acetic acid aqueous solution, and constantly stir and make it dissolving and get final product.
Cofabrication CCA antiseptic solution, compound concentration are 0.75%, 1.50% and 3.00% CCA solution, and handle Pinus massoniana Lamb timber, and compound method is with embodiment two.
D, sample impregnate processing
Sample preparation, dip treating and Anti-lost test all working and relevant calculation formula are all with embodiment three.
The sterilization of E, sample and inoculation
(Poria placenta) is inoculated on the maltose nutrient agar with the rotten transverse hole fungus of cotton, and cultivation 5-9d (temperature: 27 ± 2 ℃, relative humidity: 70 ± 5%), stand-by.
Get the clean Erlenmeyer flask of 250ml several, put one and the sizable filter paper in the bottle end in each bottle, add 5ml distilled water respectively, then same group of test block put into, seal with sealing film, and mark, place the vapor sterilization pot 20min (0.1Mpa that sterilizes with water resistant ink, 121 ℃), carry out the sample sterilization.
To on above-mentioned maltose nutrient agar, cultivate the brown rot fungus colony edge of 5-9d, buy the bacterium cake that cut-off directly is 1cm respectively, be inoculated into three feed wood chip central authorities in the 500ml Erlenmeyer flask that river sand sawdust substratum is housed, seal with punch tool.
F, the rotten experiment of sample
The culturing bottle that fills sample is positioned in the culturing room cultivates, keep 28 ± 2 ℃ of temperature, relative humidity 70 ± 5% is covered by mycelia fully up to the feed wood chip.Test block after will sterilizing then is placed on the interior feed wood chip of Erlenmeyer flask (cross section of test block contacts with the feed wood chip that is covered by mycelia), continues to cultivate in culturing room (humiture is the same).After three months, take out test block, carefully scrape off the mycelia and the impurity on surface, dry by the fire to over dry after air-dry, weigh, the heavy T of the rotten back of Pinus massoniana Lamb timber over dry
5Rate of weight loss after (4) calculating by formula is rotten.
G, sanitas preservative effect
The anti-white rot experimental result of chitosan zinc salt (CZS) timber is as shown in table 2.Compare with CCA, the metal ion fixation rate of chitosan zinc salt all increases, and preservative effect when the chitosan copper salt concn reaches 0.10%, just reaches corrosion resistant I level.
Anti-brown rot concentration of treatment of table 2 chitosan zinc salt timber and preservative effect (Pinus massoniana Lamb timber)
| The sanitas title | Concentration of preservatives (%) | Metal ion fixation rate (%) | Rotten back weightless (%) | The corrosion resistant grade |
| Be untreated | 0 | 0 | 35.65 | V |
| CZS | 0.01 | 76.39 | 12.24 | II |
| CZS | 0.10 | 82.45 | 9.14 | I |
| CZS | 0.34 | 86.83 | 4.58 | I |
| CZS | 1.02 | 88.73 | 3.30 | I |
| CZS | 2.70 | 86.46 | 1.18 | I |
| CCA | 0.75 | 73.80 | 4.71 | I |
| CCA | 1.50 | 73.19 | 4.61 | I |
| CCA | 3.00 | 77.11 | 5.58 | I |
Remarks: the corrosion resistant grade according to foxy after percentage loss of weight divide, wherein to softwood:
Corrosion resistant I:0-10%; Corrosion resistant level II:11-20%; Corrosion resistant III:21-30% slightly; Corrosion resistant IV not:＞30%
Claims (6)
1, a kind of preparation method of chitin metal salt wood preservative, at least a chitosan of adding or chitosan derivatives are dispersed in the water in water, under the heated and stirred, add at least a copper, the zinc of being selected from or/and the metallic salt of rare earth makes it dissolving in 35-60 ℃ of water-bath, wherein the ratio of chitosan and metallic salt is 1: 0.3-2.5 (W/W), stir after 1.5-5 hour and take out, supernatant liquor is abandoned in centrifugation, and it is colourless to be washed with distilled water to supernatant liquor, dry under 55-75 ℃, get meal; In powder, add acid, stir and make it dissolving, and adjusting pH value is 2-6.
2, preparation method as claimed in claim 1; it is characterized in that described chitosan and chitosan derivatives are chitosan, water-soluble chitosan, cm-chitosan, N-acetylated chitosan sugar, N-propionyl chitosan, N-Butyrylation chitosan, N-hexanoyl chitosan, the adjacent benzyl chitosan of N-and/or N-carboxyl chitosan.
3, preparation method as claimed in claim 1 is characterized in that, the metallic salt of described cupric, zinc comprises cupric or/and the vitriol of zinc, phosphoric acid salt, hydrochloride or nitrate.
As claim 1 or 3 described preparation methods, it is characterized in that 4, described rare earth metal salt is that rare earth chloride, rare-earth phosphorate are or/and rare earth nitrate.
5, preparation method as claimed in claim 1 is characterized in that, described acid is hydrochloric acid, nitric acid, formic acid, acetate, citric acid, Mono Chloro Acetic Acid, pyruvic acid, lactic acid or phenylformic acid.
6, preparation method as claimed in claim 1 is characterized in that, the concentration of described chitin metal salt is 0.1-20%.
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