CN110450252A - Application and preparation method of the multi-functional environment-protection without urea formaldehyde timber pickling modifying agent - Google Patents

Application and preparation method of the multi-functional environment-protection without urea formaldehyde timber pickling modifying agent Download PDF

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Publication number
CN110450252A
CN110450252A CN201910857126.3A CN201910857126A CN110450252A CN 110450252 A CN110450252 A CN 110450252A CN 201910857126 A CN201910857126 A CN 201910857126A CN 110450252 A CN110450252 A CN 110450252A
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parts
added
urea
modifying agent
preparation
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Inventor
吕文华
刘强强
石媛
杜浩佳
倪林
柴宇博
刘君良
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Research Institute of Wood Industry of Chinese Academy of Forestry
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Research Institute of Wood Industry of Chinese Academy of Forestry
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Priority to CN201910857126.3A priority Critical patent/CN110450252A/en
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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
    • B27K3/005—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising microparticles
    • 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
    • B27K3/02—Processes; Apparatus
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • 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
    • B27K5/04—Combined bleaching or impregnating and drying of wood
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C08G12/36—Ureas; Thioureas
    • C08G12/38—Ureas; Thioureas and melamines
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

A kind of application and preparation method the present invention relates to multi-functional environment-protection without urea formaldehyde timber pickling modifying agent, multi-functional environment-protection is without urea formaldehyde timber pickling modifying agent, including following raw materials: melamine, glucose, glyoxal, ethyl alcohol, urea, toughener, acidic catalyst, activator, basic catalyst, aqueous solution of inorganic matter, fire retardant, fungusproof anti-corrosion agent.Preparation method: water is added into reaction kettle, open agitating function, glucose is taken to be added in reaction kettle, melamine is continuously added after heating, acidic catalyst, which is then added, makes the reacting liquid pH value in reaction kettle in acidity, continues to heat up, and urea is added, monitoring addition alkaline conditioner through color after heating up again makes reacting liquid pH value in reaction kettle terminate reaction in alkalinity, and stopping heats and carries out cooling and handling to obtain dipping stoste.The present invention can be fully penetrated to fast growing wood progress, significantly improves wood performance, through the modified artificial forest fast growing wood of this method, has environmentally protective, moderate cost, density is big, and intensity is high, good toughness, and dimensionally stable is fire-retardant, the advantages that fungus-proof antisepsis, processing performance is good, Color tunable, added value is high.

Description

Application and preparation method of the multi-functional environment-protection without urea formaldehyde timber pickling modifying agent
Technical field
The invention belongs to the environmentally friendly nothings that one kind can carry out multi-functional dipping modification to biological materials such as wood bamboo rattan materials The preparation method and its efficient application technology of urea formaldehyde modifying agent.
Background technique
Timber is unique recyclable organism engineering material, and is a kind of ecological environment material nd, has carbon sequestration, power consumption of polymer processing Less, environmental pollution is small, can the environment compatibilities such as natural degradation and recycling.As the mankind are continuously increased timber demand, The worsening shortages of timber resources, using the processing of the methods of chemistry, physics or machinery or processing timber and wood materials, improvement wood Material property assigns timber new function, to open up the frontier of wood utilization, realizes that efficient utilize of timber has become very Important real project.
China's artificial forest area ranks first in the world, since that there are density is small, material is soft, intensity is low etc. lacks for artificial forest wood It falls into, needs to carry out enhancing modification, be just able to achieve its high value added utilization.By carrying out chemical functional improvement to timber, change Its added value of product can be improved in the dimensional stability and durability of kind timber, the service life of prolonging wood, realizes artificial forest money The efficient utilization in source.
The natural porous of timber is configured with filling-modified conducive to impregnate to it.Using the organic list of the small molecules such as acetic anhydride The impregnated timbers such as body, water-soluble low molecular weight resin prepolymer, are then solidified or are polymerize, in dipping and solidification process by It is volatile in organic monomer and easily cause environmental pollution, such as Lauxite, phenolic resin, melamine resin are preparing and are making With there is Form aldehyde release in the process, environment is adversely affected；And organic monomer, resinae product price are higher, lead to wood Material is modified higher cost.With the precursor liquids impregnated timber such as inorganic salts, although timber is in hardness, intensity, anti-flammability and wearability etc. Aspect has certain improvement, but material fragility increases, and toughness decline, moisture-proof water resistance is bad, reduces the service performance of timber. Inorganic component is blended with organic component prepares Wooden modifying liquid, complicated component, due to existing between inorganic component and organic component Interface compatibility problem, it is unstable that microphase-separated will lead to precursor liquid, so that improved wood performance is unstable.Timber pickling is modified Technique often includes two stages of impregnation and dry solidification.The dimensionally stable of timber can be effectively improved by heat treatment method Property, but when temperature is higher, will cause portion of cellulose degradation to damage its mechanical strength.
Thus, the shorter modified existing poor permeability of timber pickling, working life, higher cost, crisp need to be urgently solved at present Property larger, not wet-heat resisting and there are the small molecules such as formaldehyde to discharge the pollution main problems such as environment during making and using.
Summary of the invention
The present invention provides a kind of application and preparation method of the multi-functional environment-protection without urea formaldehyde timber pickling modifying agent, has raw material Resourceful, environmentally friendly, at low cost, the formaldehydeless release of production, good penetrability, simple process, curing performance is good and can significantly change While the physical and mechanical property and dimensional stability properties of kind fast growing wood, assign fast growing wood excellent fire-retardant, mould proof, anti-corrosion With the multi-functional characteristic such as incrustation, the advantages of greatly promoting timber service performance and prolonging wood service life.
A kind of multi-functional environment-protection is without urea formaldehyde timber pickling modifying agent, the raw material including following weight proportion:
10~20 parts of melamine, 10~120 parts of glucose, 10~60 parts of glyoxal, 10~60 parts of ethyl alcohol, urea 10~80 Part, 1~6 part of toughener, 1~5 part of acidic catalyst, 1~20 part of activator, 1~6 part of basic catalyst, aqueous solution of inorganic matter 7 ~20 parts, 1~5 part of fire retardant, 1~5 part of fungusproof anti-corrosion agent.
Preferred embodiment includes that the weight proportion of each raw material is:
15~18 parts of melamine, 20~100 parts of glucose, 20~50 parts of glyoxal, 20~50 parts of ethyl alcohol, urea 20~70 Part, 2~5 parts of toughener, 3~5 parts of acidic catalyst, 5~15 parts of activator, 3~6 parts of basic catalyst, aqueous solution of inorganic matter 9 ~18 parts, 2~4 parts of fire retardant, 2~4 parts of fungusproof anti-corrosion agent.
Method of the invention has the following steps:
1) it matches and stocks up according to following weight:
10~20 parts of melamine, 10~120 parts of glucose, 10~60 parts of glyoxal, 10~60 parts of ethyl alcohol, urea 10~80 Part, 1~6 part of toughener, 1~5 part of acidic catalyst, 1~20 part of activator, 1~6 part of basic catalyst, aqueous solution of inorganic matter 7 ~20 parts, 1~5 part of fire retardant, 1~5 part of fungusproof anti-corrosion agent;
(2) glucose is added in reaction kettle, is warming up to 50~70 DEG C, melamine is added and accounts for melamine parts by weight 10 ~30% toughener, acidic catalyst, which is added, makes the reacting liquid pH value 3~5 in reaction kettle, is warming up to 70~90 DEG C, reaction 1 ~2h；
(3) temperature of reaction kettle is reduced to 60~70 DEG C, glyoxal and ethyl alcohol is added, basic catalyst is added and adjusts pH value of solution Value is 6~7, and temperature is controlled at 60~80 DEG C, reacts 0.5~1.0h；
(4) be first added and account for the urea of weight of urea part 70~90%, be warming up to 80~90 DEG C, react 1h, reduce temperature to 70~ 80 DEG C, remaining urea is added, adjusting solution pH value is 6~7, and the reaction was continued;
(5) when the mixing multiple of reaction solution and water is 1:5~10,40~60 DEG C are cooled to, addition accounts for mixeding liquid volume 3~6% Activator, reduce temperature to 40 DEG C hereinafter, obtain high osmosis without urea formaldehyde timber pickling modifying agent；
(6) water will be added without urea formaldehyde timber pickling modifying agent, and will be deployed into the aqueous solution that mass fraction is 10~30%, addition accounts for water The aqueous solution of inorganic matter of liquor capacity 2~10% accounts for the functions such as fire-retardant/anti-corrosion/mould proof/dyestuff of aqueous solution volume 0.1~10% Property auxiliary agent, be uniformly mixed, obtain multi-functional no urea formaldehyde timber pickling modifying agent；
(7) the dry artificial forest wood of gas is placed in closed impregnation tank, using vacuumizing -0.08 to -0.10MPa, pressure maintaining 0.5~1.0h, release, 0.8~1.2MPa of repressurization after release, 1~4h of pressure maintaining repeat 2~4 times, are sufficiently submerged in modifying agent It discharges after timber；
(8) material stacking will be handled, gas is done to moisture content 40~60%, and the softer gradient increased temperature drying process of use carries out kiln drying, does 40~160 DEG C of dry temperature, it is dry to moisture content about 20~30% or so；
(9) using superheated vapour as heat transfer medium, 140~220 DEG C are warming up to, keeps the temperature 1~5h depending on plate thickness, it is cooled to 50~ It is 70 DEG C, dry to whole moisture content 8~12%, obtain environment protection multifunctional dipping improved wood.
The toughener is polyethylene glycol, polysiloxanes, polyvinyl alcohol, diethylene glycol (DEG), vinylacetate, acrylic acid second One of ester, polyacrylamide, Sodium Polyacrylate, styrene-acrylic emulsion, methyltriethoxysilane or a variety of combinations.
The acidic catalyst be hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, citric acid, ammonium chloride, copper sulphate, ammonium nitrate, sulphur One of sour nickel, ammonium chloride, ammonium nitrate, oxalic acid, acetic acid, itaconic acid or a variety of combinations.
The basic catalyst is one of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate or more The combination of kind.
The activator is amino silane, alkyl benzene sulphonate ammonium, ammonium lignosulphonate, sodium lignin sulfonate, alkylnaphthalene Sodium sulfonate, alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, neopelex, trimethyl chlorination One of ammonium is a variety of and combinations thereof.
The aqueous solution of inorganic matter is sodium silicate, potassium water glass, lithium silicate, nano silica, nano-silica Change one of titanium, Nano zinc dioxide impact-resistant, nano montmorillonite or a variety of combinations.
The fire retardant is boric acid, borax, dicyandiamide, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, low-polymerization-dammonium ammonium polyphosphate One of or a variety of combinations.
The fungusproof anti-corrosion agent is boric acid, borax, ammoniacal copper quaternary, Tebuconazole, propiconazole, Cyproconazole, Boron tribromide, two One of decyl dimethyl ammonium chloride, hexadecyltrimethylammonium chloride or a variety of combinations.
The artificial forest wood is the fast growing woods such as poplar, rubber wood timber, China fir, the pine of artificial growth.
There are raw material resources to enrich, produce environmentally friendly, at low cost, formaldehydeless release, good penetrability, simple process by the present invention, Curing performance is good and can assign fast-growing while the physical and mechanical property and dimensional stability properties for significantly improving fast growing wood The multi-functional characteristic such as excellent fire-retardant, the mould proof, anti-corrosion of material and incrustation, greatly promoting timber service performance and prolonging wood makes The advantages of with the service life.
The present invention can be fully penetrated to the timber progress that hardly possible is impregnated, and wood performance is significantly improved, through the modified people of this method Work woods softwood has density big, and intensity is high, and good toughness, dimensionally stable is fire-retardant, fungus-proof antisepsis, good decorative property, processability The advantages that energy is good, production environmental protection, using effect is good, and added value is high.
Treated softwoods such as Cunninghamia lanceolata, poplar modified by this invention, most prominent advantage is that density is big, by force Degree is high, and good toughness, dimensionally stable is fire-retardant, fungus-proof antisepsis, and processing performance is good, ecological, environmental protective, can be directly used for solid wooden floor board, door The processing of the high value added products such as window, furniture, decorative wall panels, and water-soluble dye can be added as needed and assign processing material dyeing Etc. other functions, Vehicles Collected from Market is adapted to completely to the multifunction demand of improved wood.Present embodiments can apply to poplars, rubber The artificial forest fast growing wood such as wood, China fir, pine, greatly promotes its utility value and added value of product.
The high osmosis is tested according to GB/T 14074~2017 " adhesion agent for wood industry and its resin method of inspection " Performance indexes of the environment protection multifunctional without urea formaldehyde timber pickling modifying agent is as follows:
Appearance: pale yellow transparent homogeneous liquid；
Solid content: 45~55%；
PH value: 7~8；
Viscosity (23 DEG C): 3~7 mPa.s；
Water mixing multiple: > 10 times；
Storage period: greater than 50 day.
Specific embodiment
Embodiment 1:
(1) it matches and stocks up according to following weight:
It is 1:1~12:1~6:1~6:1~8 proportion according to melamine, glucose, glyoxal, ethyl alcohol, urea mol ratio Stock.
(2) glucose is added in reaction kettle, is warming up to 50~70 DEG C, melamine is added and accounts for melamine weight The toughener of part 10~30%, acidic catalyst, which is added, makes the reacting liquid pH value 3~5 in reaction kettle, is warming up to 70~90 DEG C, React 1~2h.
(3) temperature of reaction kettle is reduced to 60~70 DEG C, glyoxal and ethyl alcohol is added, it is molten that basic catalyst adjusting is added Liquid pH value is 6~7, and temperature is controlled at 60~80 DEG C, reacts 0.5~1.0h.
(4) urea for accounting for weight of urea part 70~90% is first added, is warming up to 80~90 DEG C, reacts 1h, reduces temperature extremely 70~80 DEG C, remaining urea is added, adjusting solution pH value is 6~7, and the reaction was continued.
(5) when the mixing multiple of reaction solution and water is 1:5~10,40~60 DEG C are cooled to, addition accounts for mixeding liquid volume 3 ~6% activator, reduce temperature to 40 DEG C hereinafter, obtain high osmosis without urea formaldehyde timber pickling modifying agent.
(6) water will be added without urea formaldehyde timber pickling modifying agent, and will be deployed into the aqueous solution that mass fraction is 10~30%, be added The aqueous solution of inorganic matter for accounting for aqueous solution volume 2~10% accounts for fire-retardant/anti-corrosion/mould proof/dyestuff of aqueous solution volume 0.1~10% etc. Functional aid is uniformly mixed, obtains multi-functional no urea formaldehyde timber pickling modifying agent；
(7) the dry artificial forest wood of gas is placed in closed impregnation tank, using vacuumizing -0.08 to -0.10MPa, pressure maintaining 0.5~1.0h, release, 0.8~1.2MPa of repressurization after release, 1~4h of pressure maintaining repeat 2~4 times, are sufficiently submerged in modifying agent It discharges after timber；
(8) material stacking will be handled, gas is done to moisture content 40~60%, and the softer gradient increased temperature drying process of use carries out kiln drying, does 40~160 DEG C of dry temperature, it is dry to moisture content about 20~30% or so；
(9) using superheated vapour as heat transfer medium, 140~220 DEG C are warming up to, keeps the temperature 1~5h depending on plate thickness, it is cooled to 50~ It is 70 DEG C, dry to whole moisture content 8~12%, obtain environment protection multifunctional dipping improved wood.
Embodiment 2: 20kg glucose and 20kg water are added in reaction kettle, and stirring is warming up to 60 DEG C, and 2kg melamine is added Amine and 0.15kg polyvinyl alcohol, 0.35kg polyethylene glycol, are warming up to 75 DEG C, stir evenly, and 2kg ammonium chloride, 0.5kg sulfuric acid is added Copper, adjusting reacting liquid pH value is 3.5, is warming up to 90 DEG C, reacts 1.5h；Temperature of reaction kettle is reduced to 75 DEG C, 1.5kg second two is added Aldehyde and 1.2kg ethyl alcohol, it is 6.5 that sodium hydroxide, sodium carbonate and ammonium hydroxide, which is added, and adjusts solution ph, and temperature controls the reaction at 65 DEG C 40min；1kg urea is added, is warming up to 85 DEG C, reacts 1h, reduces temperature to 75 DEG C, 0.5kg urea is added, adjust solution PH Value is 7, and the reaction was continued.When the mixing multiple of reaction solution and water is 1:10,50 DEG C are cooled to, the poly alkyl alcohol of 1.2kg is added The amino silane of ethylene oxide ether and 0.3kg reduces temperature to 50 DEG C；Add water 50kg water, be deployed into mass fraction be 25% it is water-soluble Liquid, is successively added 1kg dimercaptodimethyl ammonium chloride and the sodium silicate of 5kg is sufficiently miscible；It is eventually adding 1kg boric acid and 3kg Borax is sufficiently miscible, obtains multi-functional no urea formaldehyde timber pickling modifying agent.
It is 2000mm × 200mm × 25mm(longitudinal × tangential × radial by specification), the artificial forest that moisture content is 9~12% China fir and poplar distinguish stacking, are fixed in impregnation tank, using vacuumize -0.10MPa → pressure maintaining 25min → release → plus 1.2MPa → pressure maintaining 2h treatment process is pressed, is repeated 3 times, modifying agent is made to be sufficiently submerged in timber；Processing material is taken out, gas does 5 days extremely 55% or so moisture content moves into heat treatment dry kiln；Gradient type heating drying, every 4h increase 10 DEG C of temperature, and drying about 3 days reaches 20% or so moisture content；By hot water and steam, 180 DEG C are risen to the heating rate of 10 DEG C/h, keeps the temperature 3h, is cooled to 60 DEG C, drying To whole moisture content 10% or so, environment protection multifunctional dipping improved wood is obtained.
The high osmosis is tested according to GB/T 14074~2017 " adhesion agent for wood industry and its resin method of inspection " Performance indexes of the environment protection multifunctional without urea formaldehyde timber pickling modifying agent is as follows:
Appearance: pale yellow transparent homogeneous liquid；
Solid content: 50%；
PH value: 7.6；
Viscosity (23 DEG C): 5.5 mPa.s；
Water mixing multiple: 10 times；
Storage period: 53 days.
According to items of the standard methods such as GB/T 1927-2009~GB/T 1943-2009 to Wooden modifying before and after the processing Physical and mechanical property indexs are detected, as a result as follows:
Poplar wood in plantation handles material: timber averagely inhales dose up to 258%, and average growth rate is up to 63%, average moisture content 9%, density by 0.396g/cm before processing3Increase to 0.646g/cm3；Swollen rate is resisted to promote 61% or more；Deflection Modulus of Elasticity is increased by 8.3Gpa To 12.7Gpa；Bending strength increases to 109Mpa by 57Mpa；Compression strength increases to 59Mpa by 28Mpa；Surface hardness by 1347N increases to 3751 N；Impact flexibility is by 21.4 KJ/m2Increase to 22.7 KJ/m2；Oxygen index (OI) is promoted by 24% to 53%； Fungus-proof antisepsis is functional.
Cunninghamia lanceolata handles material: timber averagely inhales dose up to 227%, and average growth rate is up to 55%, average moisture content 10%, Density is by the 0.361g/cm before handling3Increase to 0.560g/cm3；Resist swollen rate that can promote 55% or more；Deflection Modulus of Elasticity by 5.2Gpa increases to 8.6Gpa；Bending strength increases to 85.6Mpa by 48.8Mpa；Compression strength increases to 49Mpa by 24Mpa； Surface hardness increases to 2657 N by 1123N；Impact flexibility is by 20.5KJ/m2Increase to 22.1KJ/m2, oxygen index (OI) mentions by 23% It is raised to 51%；Fungus-proof antisepsis is functional.
Treated softwoods such as Cunninghamia lanceolata, poplar modified by this invention, most prominent advantage be it is environmentally protective, Moderate cost, density is big, and intensity is high, and good toughness, dimensionally stable is fire-retardant, fungus-proof antisepsis, has good color and processability Can, it can be directly used for the processing of the high value added products such as solid wooden floor board, door and window, furniture, decorative wall panels, but also can add as needed Enter water-soluble dye to dye processing material, is able to satisfy domestic and international consumption market to the multifunction demand of improved wood.This Invention may be used on the artificial forest fast growing wood such as poplar, rubber wood timber, China fir, pine, greatly promotes its utility value and product is attached It is value added.
In short, the present invention can be fully penetrated to fast growing wood progress, wood performance is significantly improved, through the modified people of this method Work woods fast growing wood, has environmentally protective, and moderate, density is big, and intensity is high, and good toughness, dimensionally stable is fire-retardant, mould proof anti- The advantages that corruption, processing performance is good, Color tunable, added value is high.

Claims (10)

1. a kind of multi-functional environment-protection is without urea formaldehyde timber pickling modifying agent, it is characterised in that the raw material including following weight proportion:
10~20 parts of melamine, 10~120 parts of glucose, 10~60 parts of glyoxal, 10~60 parts of ethyl alcohol, urea 10~80 Part, 1~6 part of toughener, 1~5 part of acidic catalyst, 1~20 part of activator, 1~6 part of basic catalyst, aqueous solution of inorganic matter 7 ~20 parts, 1~5 part of fire retardant, 1~5 part of fungusproof anti-corrosion agent.
2. multi-functional environment-protection according to claim 1 is without urea formaldehyde timber pickling modifying agent, it is characterised in that including The weight proportion of each raw material is:
15~18 parts of melamine, 20~100 parts of glucose, 20~50 parts of glyoxal, 20~50 parts of ethyl alcohol, urea 20~70 Part, 2~5 parts of toughener, 3~5 parts of acidic catalyst, 5~15 parts of activator, 3~6 parts of basic catalyst, aqueous solution of inorganic matter 9 ~18 parts, 2~4 parts of fire retardant, 2~4 parts of fungusproof anti-corrosion agent.
3. a kind of prepare application and preparation method of the multi-functional environment-protection as described in claim 1 without urea formaldehyde timber pickling modifying agent, It is characterized by: it includes the following steps:
(1) it matches and stocks up according to following weight:
10~20 parts of melamine, 10~120 parts of glucose, 10~60 parts of glyoxal, 10~60 parts of ethyl alcohol, urea 10~80 Part, 1~6 part of toughener, 1~5 part of acidic catalyst, 1~20 part of activator, 1~6 part of basic catalyst, aqueous solution of inorganic matter 7 ~20 parts, 1~5 part of fire retardant, 1~5 part of fungusproof anti-corrosion agent;
(2) glucose is added in reaction kettle, is warming up to 50~70 DEG C, melamine is added and accounts for melamine parts by weight 10 ~30% toughener, acidic catalyst, which is added, makes the reacting liquid pH value 3~5 in reaction kettle, is warming up to 70~90 DEG C, reaction 1 ~2h；
(3) temperature of reaction kettle is reduced to 60~70 DEG C, glyoxal and ethyl alcohol is added, basic catalyst is added and adjusts pH value of solution Value is 6~7, and temperature is controlled at 60~80 DEG C, reacts 0.5~1.0h；
(4) be first added and account for the urea of weight of urea part 70~90%, be warming up to 80~90 DEG C, react 1h, reduce temperature to 70~ 80 DEG C, remaining urea is added, adjusting solution pH value is 6~7, and the reaction was continued;
(5) when the mixing multiple of reaction solution and water is 1:5~10,40~60 DEG C are cooled to, addition accounts for mixeding liquid volume 3~6% Activator, reduce temperature to 40 DEG C hereinafter, obtain high osmosis without urea formaldehyde timber pickling modifying agent；
(6) water will be added without urea formaldehyde timber pickling modifying agent, and will be deployed into the aqueous solution that mass fraction is 10~30%, addition accounts for water The aqueous solution of inorganic matter of liquor capacity 2~10% accounts for the functions such as fire-retardant/anti-corrosion/mould proof/dyestuff of aqueous solution volume 0.1~10% Property auxiliary agent, be uniformly mixed, obtain multi-functional no urea formaldehyde timber pickling modifying agent；
(7) the dry artificial forest wood of gas is placed in closed impregnation tank, using vacuumizing -0.08 to -0.10MPa, pressure maintaining 0.5~1.0h, release, 0.8~1.2MPa of repressurization after release, 1~4h of pressure maintaining repeat 2~4 times, are sufficiently submerged in modifying agent It discharges after timber；
(8) material stacking will be handled, gas is done to moisture content 40~60%, and the softer gradient increased temperature drying process of use carries out kiln drying, does 40~160 DEG C of dry temperature, it is dry to moisture content about 20~30% or so；
(9) using superheated vapour as heat transfer medium, 140~220 DEG C are warming up to, keeps the temperature 1~5h depending on plate thickness, it is cooled to 50~ It is 70 DEG C, dry to whole moisture content 8~12%, obtain environment protection multifunctional dipping improved wood.
4. application and preparation method according to claim 3, it is characterised in that: the toughener is polyethylene glycol, poly- silicon Oxygen alkane, polyvinyl alcohol, diethylene glycol (DEG), vinylacetate, ethyl acrylate, polyacrylamide, Sodium Polyacrylate, styrene-acrylic emulsion, first One of ethyl triethoxy silicane alkane or a variety of combinations.
5. application and preparation method according to claim 3, it is characterised in that: the acidic catalyst is hydrochloric acid, sulphur Acid, phosphoric acid, boric acid, citric acid, ammonium chloride, copper sulphate, ammonium nitrate, nickel sulfate, ammonium chloride, ammonium nitrate, oxalic acid, acetic acid, clothing health One of acid or a variety of combinations.
6. application and preparation method according to claim 3, it is characterised in that: the basic catalyst be sodium hydroxide, One of calcium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate or a variety of combinations.
7. application and preparation method according to claim 3, it is characterised in that: the activator is amino silane, alkyl Ammonium benzene sulfonate, ammonium lignosulphonate, sodium lignin sulfonate, Negel, alkyl phenol polyoxyethylene ether, fatty alcohol polyoxy second One of alkene ether, neopelex, dodecyl trimethyl ammonium chloride are a variety of and combinations thereof.
8. application and preparation method according to claim 3, it is characterised in that: the aqueous solution of inorganic matter is sodium water glass Glass, potassium water glass, lithium silicate, nano silica, nano-titanium dioxide, Nano zinc dioxide impact-resistant, one in nano montmorillonite Kind or a variety of combinations.
9. application and preparation method according to claim 3, it is characterised in that: the fire retardant is boric acid, borax, double One of cyanamide, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, low-polymerization-dammonium ammonium polyphosphate or a variety of combinations.
10. fungusproof anti-corrosion agent described in is boric acid, borax, ammoniacal copper quaternary, Tebuconazole, propiconazole, Cyproconazole, Boron tribromide, two One of decyl dimethyl ammonium chloride, hexadecyltrimethylammonium chloride or a variety of combinations.
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CN113249056A (en) * 2021-04-02 2021-08-13 中国林业科学研究院木材工业研究所 Flame-retardant luminous formaldehyde-reducing functional additive and preparation method and application thereof
EP3967468A1 (en) * 2020-09-09 2022-03-16 Georg-August-Universität Göttingen Production method for modified lignocellulose materials
CN114196161A (en) * 2021-12-17 2022-03-18 中国林业科学研究院木材工业研究所 Formaldehyde-free low-molecular-weight amino resin modifier and preparation method and application thereof
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CN111113613A (en) * 2019-12-24 2020-05-08 葛金梅 Preparation method of water-resistant heat-insulating wood floor
EP3967468A1 (en) * 2020-09-09 2022-03-16 Georg-August-Universität Göttingen Production method for modified lignocellulose materials
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CN116587385A (en) * 2023-06-27 2023-08-15 广东省林业科学研究院 Application of glyoxal-acrylamide compound liquid
CN116587385B (en) * 2023-06-27 2024-02-13 广东省林业科学研究院 Application of glyoxal-acrylamide compound liquid
CN116876254A (en) * 2023-07-10 2023-10-13 上海昶法新材料有限公司 Rosin/glucose urea resin composite sizing agent and preparation method thereof

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