CN107030818B - A kind of preparation method of mildew-proof flame retarded composite wood modifying agent and improved wood - Google Patents
A kind of preparation method of mildew-proof flame retarded composite wood modifying agent and improved wood Download PDFInfo
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- CN107030818B CN107030818B CN201610861826.6A CN201610861826A CN107030818B CN 107030818 B CN107030818 B CN 107030818B CN 201610861826 A CN201610861826 A CN 201610861826A CN 107030818 B CN107030818 B CN 107030818B
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- mildew
- flame retarded
- retardant
- timber
- wood
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/007—Treating of wood not provided for in groups B27K1/00, B27K3/00 using pressure
- B27K5/0075—Vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/20—Removing fungi, molds or insects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/30—Fireproofing
Abstract
The invention discloses a kind of mildew-proof flame retarded composite wood modifying agent, including chitosan silver complex and nitrogen phosphorus or nitrogen phosphorus boron fire retardant preservative solution, wherein the mass ratio of retardant solution and chitosan silver complex is 100:0.1-1.Another aspect of the present invention discloses the preparation method of the mildew-proof flame retarded composite wood modifying agent, it may be assumed for preparing chitosan silver complex and retardant solution respectively, then mixes in proportion to obtain the final product；And the method for this kind of mildew-proof flame retarded composite modifier processing timber, including vacuum impregnation processing and re-dry processing are carried out to timber.The present invention, which combines wood mould and Wood flame-retarded technology, prepares the modifying agent and modification timber that have both mould proof and fire-retardant double grading, improves the production efficiency of Wooden modifying, increases the safety in utilization and added value of product.
Description
Technical field
The present invention relates to a kind of mildew-proof flame retarded composite wood modifying agent and preparation method thereof, belong to mould proof, flame-retardant modified place
Manage technical field.
Background technique
A kind of recyclable materials of the timber as excellent environmental protection, are widely used in building, the industries such as furniture.However, wooden
Material itself has some defects, and limits its application development.On the one hand, timber has inflammability, this is also to induce fire
One of the reason of；On the other hand, monosaccharide, starch, hemicellulose and moisture etc. are contained in timber and acidity value pH is 4.0~6.5,
It is created condition for the growth of mould, therefore timber is easy to happen and goes mouldy and cause sapstain, influences the beauty of timber.This
Outside, mould grows in environment indoors also can bring hidden danger to human health.Chitosan is from the Crustaceanses crust such as shrimp, crab
A kind of natural alkaline macromolecule polysaccharide of middle extraction, can influence the plasma membrane property of fungi, have certain antibiotic property.Fire-retarding of wood
Processing is to improve the important means of wooden material fireproof safety, and traditional halogen type fire retardant can generate greatly in combustion
Pernicious gas is measured, has been forbidden to use at present.Nitrogen phosphorus flame retardant is because having many advantages, such as that small toxicity, price are low, treatment process is simple
Wood fire retardant as mainstream.
The Chinese patent application of Publication No. CN 101323121A discloses that " modified chitosan metal composite timber is anti-
Rotten agent and its manufacturing method ", the preservative is by 16-30 parts of bactericidal properties metal salts, 15-25 parts of chitosans, 6-18 parts of sodium perborate
And its esters, 250-300 part deionized water, 2-4h is stirred to react at 30-60 DEG C, it is white or green after wherein solid matter is dry
The modified chitosan metal complexes of color or grey powder；Matched again with the 0.5-5 parts of complexs and 0.5-2 parts of acid, 100 parts of water
Timber preservative aqueous solution is made.The modified chitosan metal composite of the patent disclosure can be used immersion, brushing, spray, add
The a variety of methods of impregnating are pressed to carry out anti-corrosion, mould proof, insect-prevention treatment to timber or bamboo wood etc..103858933 A's of Publication No. CN
It is compound anti-that Chinese patent " a kind of preparation method of anti-tarnish chitosan-silver complex antimicrobials " discloses anti-tarnish chitosan-silver
The preparation method of microbial inoculum including configuring the acid solution of chitosan, and forms chitosan solution after filtering out insoluble matter therein；?
Silver salt solution is added in chitosan solution, is thoroughly mixed uniformly, adds silver salt with the reducing agent of silver salt equimolar ratio
It is reduced into nano silver colloidal sol and stirs；A certain amount of chlorauric acid solution is added dropwise in nano silver colloidal sol, nano silver is replaced
Gold-plated reaction continues to stir.The complex antimicrobials of the patented invention are suitable for the antibacterial of light coloured fabrics, dressing, packaging material etc.,
There is good killing effect to multi-cultur es such as common Escherichia coli, staphylococcus aureuses, while being effective against discoloration
Influence to fabric whiteness and appearance.
In addition, the Chinese patent application of Publication No. CN 104210002A discloses " a kind of composite flame-retardant agent, preparation side
Method and application thereof ", a kind of composite flame-retardant agent of the disclosure of the invention, including polysilicon acid phosphate dihydrogen aluminum solution and nitrogen phosphorus fire retardant are molten
Liquid prepares polysilicon acid phosphate dihydrogen aluminum solution and nitrogen phosphorus fire retardant solution respectively, then the two is mixed to obtain the final product, the composite flame-retardant agent
With apparent flame-retardant smoke inhibition effect.The Chinese patent application of Publication No. CN 101665588A discloses a kind of " biodegrade
Fire proofing and preparation method thereof ", the Biodegradable flame resistance material of the invention, using starch and chitosan as main component, with red
Phosphorus is flame retardant, and starch/chitosan provides a large amount of carbon sources, nitrogen itself is contained in chitosan, but after addition acid source red phosphorus,
The flame retardant property of biodegradable material is effectively improved, the use scope of degradation material is extended.Publication No. CN
The Chinese patent application of 105619558A discloses that " the super-hydrophobic oleophobic antimycotic antiseptic flame-proof weather-resisting timber of hybrid inorganic-organic changes
Property agent preparation method ", Wood modifier is mixed by organoalkoxysilane, deionized water and dehydrated alcohol in the invention, then
The reactions such as functional reagent, fluorine containing silane coupling agent, curing agent are added to be made, the wood surface of invention modifier modification processing is quiet
State water contact angle can be up to 150 ° or more, roll angle is less than 10 °；The edible oil contact angle on improved wood surface be up to 120 ° with
On, there is fuel shedding quality；And the antisepsis and sterilization performance of improved wood improves 90% or more, weatherability improves 10 times；Taper amount
The heat release rate peak value of hot instrument test improves 22% compared with unseasoned timber, and oxygen index (OI) improves 8.9 compared with unseasoned timber, resistance
Combustion performance has clear improvement.
In short, published patent is fire-retardant to improve mainly for the antibacterial modified processing of timber or introducing auxiliary component at present
Performance；Or for fire-retarding of wood performance enhancement but it is not directed to the additional properties improvement such as mould proof, modifying agent performance is single.It there is no behaviour
Make simple, environmental-friendly, low in cost and have both excellent mould proof, flame retardant property Wood modifier, the present invention utilizes chitosan
Enhance its mould proof fungicidal properties and chitosan as nitrogen source to nitrogen phosphorus or nitrogen phosphorus boron fire retardant preservative with the coordination of metal ion
The humidification of flame retardant property uses the green materials such as chitosan and nitrogen phosphorus or nitrogen phosphorus boron fire retardant preservative for primary raw material, system
The standby wood composite modifying agent for having both mould proof, fire-retardant double grading, and timber is handled using vacuum infusion techniques, simple process can
Row, high production efficiency, it is mould proof, flame retardant effect is excellent, the safety in utilization and added value of modification timber are greatly improved, is opened up
The application field of wide improved wood.
Summary of the invention
The purpose of the present invention is prepare it is a kind of have both mould proof and flame retardant effect Wood modifier and preparation modification wood
Material method, at the same solve timber easily go mouldy, incendive defect.The present invention uses the complexing of chitosan and metal ion anti-first
Chitosan metal complexes should be made, then compounded with fire retardant, be provided simultaneously with mould proof and fire-retardant dual spy to obtain
The composite wood modifying agent of property.
To achieve the purpose of the present invention, one aspect of the present invention provides the preparation method of mildew-proof flame retarded composite wood modifying agent,
It is coordinated including chitosan and metal ion, then is compounded with fire retardant.
A kind of mildew-proof flame retarded composite wood modifying agent is prepared, includes the steps that following sequence carries out:
1) chitosan metal complexes are made by the complex reaction of chitosan and metal ion；
2) phosphoric acid and urea reaction is made to prepare nitrogen phosphorus fire retardant；
3) guanylurea phosphate and boric acid are uniformly mixed according to certain mass ratio, nitrogen phosphorus boron fire retardant preservative is made；
4) chitosan metal complexes are compounded with the retardant solution of 2) preparation, obtains mildew-proof flame retarded composite wood
Modifier solution MP-FR1；
5) chitosan metal complexes are compounded with the retardant solution of 3) preparation, obtains mildew-proof flame retarded composite wood
Modifier solution MP-FR2；
Wherein, chitosan metal complexes described in step 1) include the chitosan-metals complex compound such as silver ion, copper ion,
Preferably chitosan silver complex.
Wherein, chitosan silver complex is made of the silver nitrate solution containing metal silver ion and carboxymethyl chitosan.
Wherein, 1.0g carboxymethyl chitosan is added to preparing the nitric acid silver analysis pure solution for being configured to 0.1mol/L
35ml silver nitrate solution in.
In particular, pH value is adjusted to 5, it is stirred to react under the conditions of 50 DEG C 4 hours.
Especially, it is filtered after fully reacting, and is washed with dehydrated alcohol to no silver ion and detected, be dried to obtain
Coffee-like powdered chitosan silver.
Wherein, the selection nitrogen phosphorus fire retardant solution of retardant solution described in step 2 or modified nitrogen phosphorus fire retardant solution.
In particular, the nitrogen phosphorus fire retardant selects BL environmental protection fire retarding agent.
Especially, the BL environmental protection fire retarding agent is the nitrogen phosphorus flame retardant that Beijing Forestry University develops.
Wherein, the mass percent concentration of the retardant solution be 5-25%, preferably 10%.
In particular, nitrogen phosphorus fire retardant or modified nitrogen phosphorus fire retardant are mixed with water, stirs, be uniformly dissolved to get described
Retardant solution, wherein the retardant solution prepare percent concentration be 5-25%, preferably 10%.
Wherein, the nitrogen phosphorus fire retardant is prepared in accordance with the following steps:
A) prepare raw material according to following weight
Phosphoric acid (concentration 85%) 7-11
Urea 3.5-4.5
Catalyst 0.025-0.035
Wherein, catalyst includes the raw material of following weight: stannic chloride 0.8-1.2, copper sulphate 1.5-2.5, chlorination
Sodium 0.8-1.2, iron chloride 0.8-1.2, aluminum sulfate 0.8-1.2, boric acid 0.8-1.2, zinc chloride 1.5-2.5 are ground uniformly
After mix；
B phosphoric acid) is added in a kettle, stir while heating, temperature is made to rise to 50-60 DEG C；
C urea) is added, the mixture of phosphoric acid and urea is stirred, makes material distribution, be heated evenly；
D when) temperature rises to 90-120 DEG C, catalyst is added into reaction kettle, continues to heat；
E after) temperature being made to rise to 130-150 DEG C, when reactant volume increases to 2-2.5 times of original volume, stop adding
Heat；
F) product in reaction kettle is poured out, to its cooling and solidifying to get.
In particular, the mixing speed control is at 50-70 revs/min.
Wherein, compounding described in step 3) is according to (nitrogen phosphorus fire retardant solution: chitosan metal complexes) mass ratio
100:0.1-1 being mixed, preferably 100:1.
Wherein, retardant solution described in step 4) selects nitrogen phosphorus boron fire retardant preservative solution.
In particular, the nitrogen phosphorus boron fire retardant preservative selection guanylurea phosphate and boric acid compound flame retardant.
Especially, the guanylurea phosphate and boric acid are compounded according to mass ratio for 7:3-5:5, and mass ratio is further excellent
It is selected as 6:4.
Wherein, the mass percent concentration of the retardant solution be 5-25%, preferably 10%.
The present invention provides a kind of above-mentioned mildew-proof flame retarded composite modifier processing timber on the one hand, including following sequence carries out
The step of:
1) timber is immersed in mildew-proof flame retarded composite wood modifier solution, is carried out at vacuum impregnation under decompression state
Reason obtains vacuum impregnation timber；
2) impregnation timber is dried, obtains mildew-proof flame retarded composite modified timber.
Wherein, 0 MPa of vacuum degree < in vacuum impregnation treatment process described in step 1), preferably -0.01~-
0.1MPa, further preferably -0.05~-0.1MPa；Vacuum impregnation handles the time as 15-45min, preferably 20-40min.
In particular, vacuum degree is more preferably -0.05MPa, vacuum impregnation processing in the vacuum impregnation treatment process
Time is more preferably 30min.
Wherein, drying process temperature described in step 2 is 100-103 DEG C, preferably 103 DEG C；Drying time >=6h；Institute
State moisture content≤15% of flame-retardant impregnating timber, preferably 7-15%, further preferably 10%.
In particular, further including placing the timber after dipping at room temperature 5-10d(days) after, then carry out at the drying
Reason；The drying process is carried out again after preferably placing 7d.
It is handled by vacuum impregnation, the gas in timber is discharged, while mildew-proof flame retarded composite wood modifier solution fills
Divide the gap for being impregnated into wood internal, reaches higher impregnating depth.
The beneficial effects are mainly reflected as follows following aspect:
1, main raw material of chitosan and nitrogen phosphorus or nitrogen phosphorus boron fire retardant preservative are equal in the mildew-proof flame retarded composite wood modifying agent of the present invention
Belong to green material, chitosan is with after metallic silver ion coordination, and bacteriostasis property enhances and required addition chitosan silver
The ratio of complex is very low, and mildew-proof flame retarded composite modifier has good safety in utilization.
2, the mass ratio of fire retardant and chitosan silver complex is only in the mildew-proof flame retarded composite wood modifying agent of the present invention
When 100:0.1, the composite modified agent solution is obvious to Trichoderma viride and aspergillus niger bacteriostasis property, and bacteriostasis with shell it is poly-
The increase of sugared silver complex ratio and further enhance.
3, chitosan silver complex has flame retardant performance as nitrogen source in the mildew-proof flame retarded composite wood modifying agent of the present invention
There is certain chemiluminescence.
4, processing the mould proof of timber, flame retardant property is remarkably reinforced in the mildew-proof flame retarded composite wood modifying agent of the present invention, reaches
To " one multiple-effect ", simplify treatment process, reduces production cost.
Detailed description of the invention
Fig. 1 is the mould proof experiment legend of the mildew-proof flame retarded composite wood modifier treatment timber of the present invention.
Specific embodiment
Although above-mentioned elaborate the present invention, however, the present invention is not limited thereto, those skilled in the art can
It is modified with principle according to the present invention, therefore, the various modifications that all principles according to the invention carry out all should be understood as
Fall into protection scope of the present invention.
Embodiment 1 prepares mildew-proof flame retarded Wood modifier
1. preparing chitosan silver complex
1A) the pure solution for being configured to 0.1mol/L of nitric acid silver analysis；
1B) 1.0g carboxymethyl chitosan is added into prepared 35ml silver nitrate solution；
PH value 1C) is adjusted to 5, is stirred to react under the conditions of 50 DEG C 4 hours；
It 1D) is filtered after fully reacting, is washed with dehydrated alcohol to no silver ion and detected, be dried to obtain coffee color
Powdered chitosan silver.
2, nitrogen phosphorus fire retardant is prepared
2A) prepare raw material according to following weight proportion:
Phosphoric acid (concentration 85%) 750g
Urea (content 99%) 400g
Catalyst 3g
Wherein, catalyst is prepared for Beijing Forestry University's material science with technical college's environmental protection flame retardant technique center yellowish
Green pulvis, the weight of raw material are as follows: stannic chloride 1.2, copper sulphate 1.5, sodium chloride 0.8, iron chloride 1.2, aluminum sulfate
1.2, boric acid 1.2, zinc chloride 2.5, mixing after being ground uniformly；
The nitrogen phosphorus fire retardant prepared in the present invention is according to a kind of patent of invention (denomination of invention: fire retardant and preparation method thereof；
The patent No.: 200710122243.2) it is prepared.(patent No.: the fire retardant 200710122243.2) prepared is equal for patent of invention
Suitable for the present invention.
2B) raw material phosphoric acid is added in reaction kettle under stirring (reaction kettle equipped with blender, thermometer,
Pressure gauge and condenser pipe), it stirs while heating, until urine is added when rising to 60 DEG C in the temperature of material in reactor phosphoric acid
Element, continuation are heated while stirring, so that catalyst is added in the temperature of mixed material when rising to 110 DEG C, continue to add while stirring
Heat reacts mixture, until the temperature of reaction mixture is up to after 130 DEG C, observing response phenomenon while heating, with
Temperature increases, and greenish liquid gradually becomes milky dope, and foam sharply increases, and rate of rise in temperature is obviously accelerated, object
The rapid spatial expansion of material, condenser pipe has bulk gas discharge, predominantly ammonia and vapor, is absorbed with water, in reaction kettle
The volume of reactant stops heating when increasing to twice of original volume, continues to stir, and material in reactor is put by itself
Heat is in vigorous reaction, and temperature continues to rise, and tends to be steady wait react, and temperature no longer rises, and when temperature is begun to decline, shows anti-
It should finish, wherein control mixing speed is 70 revs/min；
2C) the milky dope in reaction kettle is poured out, is placed in ventilating kitchen, is cooled and solidified after 30-60 minutes,
Then the nitrogen phosphorus fire retardant FR-1 powder that powdery can be obtained is crushed with pulverizer.
3, nitrogen phosphorus boron fire retardant preservative is prepared
Guanylurea phosphate and boric acid are uniformly mixed according to mass ratio for 6:4, nitrogen phosphorus boron fire retardant preservative FR-2 powder is made；
To carry out guanylurea phosphate and boric acid in nitrogen phosphorus boron fire retardant preservative by taking 6:4 as an example according to mass ratio in the embodiment of the present invention
Illustrate, the fire retardant of other mass ratio (guanylurea phosphate is than boric acid) 7:3-5:5 is suitable for the present invention.
4. preparing mildew-proof flame retarded composite wood modifying agent
Nitrogen phosphorus fire retardant made from step 2 4A) is configured to the solution that mass percent is 10%；
4B) the nitrogen phosphorus fire retardant prepared in 4A) is compounded to obtain with chitosan silver according to mass ratio 100:0.1-1
Mildew-proof flame retarded Wood modifier MP-FR1；
Nitrogen phosphorus boron fire retardant preservative made from step 2 4C) is configured to the solution that mass percent is 10%；
4D) the nitrogen phosphorus fire retardant prepared in 4C) is compounded to obtain with chitosan silver according to mass ratio 100:0.1-1
Mildew-proof flame retarded Wood modifier MP-FR2；
It is illustrated so that the mass percent concentration of retardant solution is 10% as an example in the embodiment of the present invention, other quality
The retardant solution of percent concentration 5-25% is suitable for the present invention.
The fire retardant that progress impregnation in the present invention uses is other than nitrogen phosphorus fire retardant, modified nitrogen phosphorus fire retardant
Suitable for the present invention.Fire-retardant powder prepared by 1 step 2 of embodiment, step 3 is soluble in water, and mass percent concentration is made
For the nitrogen phosphorus fire retardant solution of 5-25%, handled for impregnation of timber.
Embodiment 2 prepares mildew-proof flame retarded composite wood modifying agent
- 1 solution of chitosan silver complex and fire retardant FR, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:0.1 is compounded to obtain composite mildewproof fire retarding wood modifying agent MP- according to mass ratio
FR1(100:0.1)。
Embodiment 3 prepares mildew-proof flame retarded composite wood modifying agent
- 1 solution of chitosan silver complex and fire retardant FR, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:0.5 is compounded to obtain mildew-proof flame retarded composite wood modifying agent MP- according to mass ratio
FR1(100:0.5)。
Embodiment 4 prepares mildew-proof flame retarded composite wood modifying agent
Chitosan silver complex and fire-retardant N P-1 solution, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:1 is compounded to obtain composite mildewproof fire retarding wood modifying agent MP-FR according to mass ratio1(100:1)。
Embodiment 5 prepares mildew-proof flame retarded composite wood modifying agent
Chitosan silver complex and fire-retardant FR-2 solution, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:0.1 is compounded to obtain composite mildewproof fire retarding wood modifying agent MP- according to mass ratio
FR2(100:0.1)。
Embodiment 6 prepares mildew-proof flame retarded composite wood modifying agent
Chitosan silver complex and retardant solution NP-2, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:0.5 is compounded to obtain composite mildewproof fire retarding wood modifying agent MP- according to mass ratio
FR2(100:0.5)。
Embodiment 7 prepares composite mildewproof fire retarding wood modifying agent
Chitosan silver complex and retardant solution NP-2, and retardant solution and shell are prepared according to step in embodiment 1
Glycan silver complex is that 100:1 is compounded to obtain composite mildewproof fire retarding wood modifying agent MP-FR according to mass ratio2(100:1)。
Embodiment 8 prepares mildew-proof flame retarded composite modifier processing timber
1, it stocks up
Select quick growth poplar wood, moisture content 7%, density 0.4g/cm3。
2, vacuum impregnation is handled
By mildew-proof flame retarded composite wood modifying agent MP-FR obtained in embodiment 21(100:0.1)Solution is poured into equipped with Fast growth poplar
In the impregnating autoclave of wood, and timber is completely soaked, connects vacuum pump；It opens vacuum pump and carries out vacuumize process, make in tank
Vacuum degree reduces and remains -0.05MPa, carries out vacuum impregnation processing to timber under a reduced pressure, and vacuum impregnation wood is made
Material, wherein the ratio between volume of timber and composite mildewproof fire retarding wood modifier solution is 1:3, and the processing time is 30min.
3, it is dried
Impregnated timber is placed into 7d under room temperature (15-30 DEG C), is subsequently placed in drying box, at 103 DEG C dry 6h with
On, flame-retardant impregnating timber is made, wherein the water content of flame-retardant impregnating timber is 7%.
Embodiment 9 prepares mildew-proof flame retarded composite modifier processing timber
1, it stocks up
Select quick growth poplar wood, moisture content 7%, density 0.4g/cm3。
2, vacuum impregnation is handled
By composite mildewproof fire retarding wood modifying agent MP-FR obtained in embodiment 31(100:0.5)Solution is poured into equipped with Fast growth poplar
In the impregnating autoclave of wood, and timber is completely soaked, connects vacuum pump；It opens vacuum pump and carries out vacuumize process, make in tank
Vacuum degree reduces and remains -0.03MPa, carries out vacuum impregnation processing to timber under a reduced pressure, and vacuum impregnation wood is made
Material, wherein the ratio between volume of timber and composite mildewproof fire retarding wood modifier solution is 1:3, and the processing time is 40min.
3, it is dried
Impregnated timber is placed into 7d under room temperature (15-30 DEG C), is subsequently placed in drying box, at 103 DEG C dry 6h with
On, flame-retardant impregnating timber is made, wherein the water content of flame-retardant impregnating timber is 7%.
Embodiment 10 prepares mildew-proof flame retarded composite modifier processing timber
1, it stocks up
Select quick growth poplar wood, moisture content 7%, density 0.4g/cm3。
2, vacuum impregnation is handled
By composite mildewproof fire retarding wood modifying agent MP-FR obtained in embodiment 41(100:1)Solution is poured into equipped with Fast growth poplar
In the impregnating autoclave of wood, and timber is completely soaked, connects vacuum pump；It opens vacuum pump and carries out vacuumize process, make in tank
Vacuum degree reduces and remains -0.07MPa, carries out vacuum impregnation processing to timber under a reduced pressure, and vacuum impregnation wood is made
Material, wherein the ratio between volume of timber and composite mildewproof fire retarding wood modifier solution is 1:3, and the processing time is 20min.
3, it is dried
Impregnated timber is placed into 7d under room temperature (15-30 DEG C), is subsequently placed in drying box, at 103 DEG C dry 6h with
On, flame-retardant impregnating timber is made, wherein the water content of flame-retardant impregnating timber is 7%.
Embodiment 11 prepares mildew-proof flame retarded composite wood modifier treatment timber
With the mildew-proof flame retarded composite wood modifying agent MP-FR of invention2(100:0.1)Solution carries out impregnation to timber, remaining
It is same as Example 8.
Embodiment 12 prepares mildew-proof flame retarded composite wood modifier treatment timber
With the mildew-proof flame retarded composite wood modifying agent MP-FR of invention2(100:0.5)Solution carries out impregnation to timber, remaining
It is same as Example 9.
Embodiment 13 prepares composite mildewproof fire retarding wood modifier treatment timber
With the mildew-proof flame retarded composite wood modifying agent MP-FR of invention2(100:1)Solution to timber carry out impregnation, remaining with
Embodiment 10 is identical.
Reference examples 1
The composite mildewproof fire retarding wood modifier solution of invention is replaced directly to soak to timber with nitrogen phosphorus fire retardant FR-1
Stain processing, remaining is same as Example 8.
Reference examples 2
The composite mildewproof fire retarding wood modifier solution of invention is replaced directly to carry out to timber with nitrogen phosphorus boron fire retardant preservative FR-2
Impregnation, remaining is same as Example 9.
Reference examples 3
Composite mildewproof fire retarding wood modifier solution of the invention is replaced to carry out impregnation to timber with distilled water, remaining
It is same as in Example 10.
The mildew-proof flame retarded composite wood modifying agent inhibition zone test of test example 1
Inhibition zone test method basic principle is that a small amount of mould inhibitor is imposed on the culture medium for be inoculated with mould, is brought into contact with training
Base is supported, after a certain period of time through the culture of fixed temperature, because the diffusion of medicament acts on, is administered around position and inhibits because killing mould
Its growth on culture medium, to produce inhibition zone.Inhibition zone test method can obtain a result within a short period of time, and
Its diameter directly reflects the anti-mold effect of mould inhibitor.Table 1 is suppression of the different ratio medicament to Trichoderma viride and aspergillus niger
Bacterium circle test result.
1 inhibition zone test result of table
Fig. 1 Result of antibacterial circle method
It learns as known from Table 1:
1, mildew-proof flame retarded wood composite modifying agent MP-FR in the present invention1There is apparent suppression to Trichoderma viride and aspergillus niger
Production is used, and when fire retardant FR -1 and chitosan silver complex mass ratio are only 100:0.1, antibacterial circle diameter respectively reaches 11 Hes
12 or more；When mass ratio is only 100:1, the antibacterial circle diameter of aspergillus niger reaches 23.
2, mildew-proof flame retarded wood composite modifying agent MP-FR in the present invention2There is apparent suppression to Trichoderma viride and aspergillus niger
Production is used, and when fire retardant and chitosan silver complex mass ratio are only 100:0.1, the inhibition zone of embodiment 8 and embodiment 11
Diameter respectively reaches 11 and 8 or more.
3, composite mildewproof fire retarding wood modifying agent MP-FR in the present invention1And MP-FR2To the antibacterial of Trichoderma viride and aspergillus niger
Loop diameter increases with the increase of chitosan silver complex additive amount.
4, fire retardant FR -1, FR-2 and distilled water used in the present invention do not inhibit Trichoderma viride and aspergillus niger
Effect, antibacterial circle diameter are 0.
The mildew-proof flame retarded composite modifier of test example 2 handles wood mould experiment
1, before essence material (quick growth poplar wood) impregnation for weighing record embodiment 9,10,12,13 and reference examples 1-3 respectively
Quality (M0, kg), volume (v, m3), wood surface extraction raffinate is dried after impregnation, weighs and record impregnation wood immediately
The quality (M1, kg) of material.
2, timber drugloading rate being calculated according to formula (1), measurement result is as shown in table 1,
Drugloading rate=(M1-M0) c/v × 100%(1)
Wherein: the quality after M1-sample dipping, unit are kilogram (kg)；Quality before M0-sample dipping, unit are
Kilogram (kg).C-liquid quality fraction, %；V-volume of sample, m3。
3, by embodiment 9,10,12,13 and the mould proof test of the cotton wood of reference examples 1-3 impregnation according to GB/T
18261-2000 " test methods that mould inhibitor prevents and treats timber mould and Stain fungi " carry out, used wood sample in test
Specification is 50mm × 20mm × 5mm(long × width x thickness), each concentration gradient sets 6 repeat samples.Sample connects bacterium culture surrounding
Afterwards, it estimates and calculates the infection area of sample and be killed value, be killed value and be classified by table 2, and calculating medicament pair according to the following formula
The preventing efficiency of mould.
E=(1-D1/D0) × 100 (2)
In formula: E --- preventing efficiency；
The average killed value of D1 --- chemicals treatment sample；
The average killed value of D0 --- untreated control sample.
The killed value grade scale of sample is as shown in table 2, and after sample connects bacterium culture four weeks, wood mould tests measurement result such as
Shown in table 3.
The killed value grade scale of 2 sample of table
Fig. 2 Standard of mould resistance values
3 wood mould test result of table
Fig. 3 Result of wood anti-mould test
It learns as known from Table 3:
1, the preventing efficiency of FR-1, FR-2 and distilled water impregnation for Trichoderma viride and aspergillus niger in reference examples 1-3
It is zero, specimen surface is all by mycotic infection.Illustrate that the timber of fire-retardant FR-1, FR-2 impregnation is still vulnerable to mycotic infection.
2, through mildew-proof flame retarded composite wood modifying agent MP-FR1And MP-FR2The Trichoderma viride of the sample of processing and aspergillus niger sense
Dye area substantially reduces, and preventing efficiency reaches sample Trichoderma viride and aspergillus niger in 50% or more, especially embodiment 13
Infecting area is 0, and prevention and treatment efficiency reaches 100%, can play fully and completely anti-mold effect.
3, mildew-proof flame retarded composite wood modifying agent MP-FR2Compared to MP-FR1Prevention and treatment of the modifying agent to Trichoderma viride and aspergillus niger
Effect is more excellent, and to 87.50% or more, anti-mold effect is excellent for sample Trichoderma viride and aspergillus niger prevention and treatment efficiency in embodiment 12.
4 composite mildewproof flame-proof modifier of test example handles fire-retarding of wood performance test
Flame retardant property test includes oxygen index (OI) test and smoke density test, and wherein oxygen index (OI) test is according to GB/T 2406.2-
2009 " plastics measure burning behavior with oxygen index method ", are tested, examination used using LFY-605 type automatic oxygen index measurer
Control gauge lattice are 15mm × 5mm × 3mm(long × width x thickness)；According to GB/T 8627-2007, " construction material burns for smoke density test
Or the smoke density test method decomposed ", it is tested using JCY-2 type smoke density tester for building material, size of sample used is
25mm × 25mm × 6mm(long × width x thickness).
The results are shown in Table 4 for oxygen index (OI) and smoke density test.
4 fire retardancy test result of table
Fig. 4 Result of flame retardancy test
It learns as known from Table 4:
1, after impregnation, the drugloading rate of mildew-proof flame retarded composite modifier processing timber is above 45 kg/ m3, preparation
Flame retardant agent content reaches not less than 30 kg/m in timber3Standard, can guarantee good flame-retardance.
2, in flammability test, mildew-proof flame retarded composite modifier MP-FR1 and MP-FR2The oxygen index (OI) for handling timber is high
In 40, reach the fire-retardant ISO material standard in LOI >=27；Smoke density grade SDR is lower than 39.19, reaches GB/T 8627-2007 and " builds
Build the smoke density test method of material combustion or decomposition " regulation (SDR≤75) requirement.
3, chitosan silver complex has chemiluminescence to phosphonium flame retardant, FR-1 and FR-2 are fire-retardant as nitrogen source
The flame retardant property of agent impregnation timber increases, and 10 sample of embodiment improves 5.23% compared to 1 oxygen index (OI) of reference examples；Implement
13 sample of example decreases compared to 2 oxygen index (OI) of reference examples, but smoke density grade test carbon left increases by 26.37%.
To sum up, mildew-proof flame retarded Wood modifier MP-FR of the invention1And MP-FR2It is good to the mould proof of timber, flame retardant effect
Good, mould proof efficiency enhances with the increase of chitosan silver complex additive amount.Required chitosan in mildew-proof flame retarded Wood modifier
Silver complex additive amount is few, while assigning FR-1, FR-2 fire retardant mildew-proof function, has certain promotion to its flame retardant property
Effect.Fire retardant and chitosan silver complex mass ratio reach mildew-proof flame retarded Wood modifier MP-FR when 100:12It is green to timber
Color trichoderma and aspergillus niger prevention and treatment efficiency reach 100%；Meanwhile oxygen index (OI) increases by 75.91% compared to untreated test specimen, smoke density is real
It tests carbon yield and is increased to 27.70% by 5.01%, it is excellent that composite modifier handles the mould proof of timber, flame retardant effect.
Claims (7)
1. a kind of preparation method of mildew-proof flame retarded composite wood modifying agent, which is characterized in that include the steps that following sequence carries out:
1) chitosan and metal silver ion are coordinated, chitosan silver CTS-Ag is made through complex reaction;
2) so that phosphoric acid and urea is carried out polymerization reaction under the effect of the catalyst and nitrogen phosphorus fire retardant powder is made, make phosphoric acid amidino groups
Urea and boric acid carry out being mixed to get nitrogen phosphorus boron fire retardant preservative powder according to mass ratio for 6:4；
3) nitrogen phosphorus or nitrogen phosphorus boron fire retardant preservative powder are dissolved in water and obtain nitrogen phosphorus fire retardant solution, chitosan silver CTS-Ag system is added
Obtain mildew-proof flame retarded composite wood modifier solution.
2. the preparation method of mildew-proof flame retarded composite wood modifying agent as described in claim 1, characterized in that step
1) CTS-Ag of chitosan silver described in is to use silver nitrate and carboxymethyl chitosan in solution ph for 5, and temperature is 50 DEG C
Under the conditions of be stirred to react 4 hours after, through suction filtration, washing and the dry powdered chitosan silver complex of coffee color obtained.
3. the preparation method of mildew-proof flame retarded composite wood modifying agent as described in claim 1, characterized in that described in step 2)
Retardant solution concentration is 5%-25%.
4. the preparation method of mildew-proof flame retarded composite wood modifying agent as described in claim 1, characterized in that described in step 2)
Retardant solution concentration is 10%.
5. the preparation method of mildew-proof flame retarded composite wood modifying agent as described in claim 1, characterized in that described in step 3)
Composite mildewproof retardant solution be by the mass ratio of retardant solution and chitosan silver complex be 100:0.1-1 answered
With what is obtained.
6. the preparation method of mildew-proof flame retarded composite wood modifier treatment timber, feature described in a kind of claim 1-5 exist
In, comprising: 60 DEG C of vacuum impregnations processing carried out to timber with the mildew-proof flame retarded composite wood modifier solution, vacuum degree is-
0.03 to -0.07MPa, the processing time is 20-60min；Impregnation timber is dried.
7. a kind of improved wood of mildew-proof flame retarded composite wood modifier treatment, characterized in that according to side as claimed in claim 6
Method is prepared.
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