CN102320069A - Brittleness inhibition method of chemical function improved wood - Google Patents
Brittleness inhibition method of chemical function improved wood Download PDFInfo
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- CN102320069A CN102320069A CN201110282322A CN201110282322A CN102320069A CN 102320069 A CN102320069 A CN 102320069A CN 201110282322 A CN201110282322 A CN 201110282322A CN 201110282322 A CN201110282322 A CN 201110282322A CN 102320069 A CN102320069 A CN 102320069A
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Abstract
The invention is a brittleness inhibition method of chemical function improved wood, and relates to a new method for wood function improvement. By toughening treatment, the negative influence of wood brittleness increase caused by modifying wood only by modified resin is reduced. The method particularly comprises the following steps of: first, preparation of a modifier; second, soaking of wood or wood base materials; third, reaction polymerization of a functional reagent om the wood or wood base materials. The used organic acid catalyst has excellent environmental protection performance, can react with hydroxyls in the modifier system and the wood so as to be fixed in the wood, has good leaching resistance, and has no environmental harm. Functionalized wood prepared by the technology of the invention has significantly improved impact strength. The impact strength of functionalized wood without toughening treatment is reduced by 75%, and the impact strength of functionalized wood with toughening treatment is reduced only by 35%. Meanwhile, the toughening treatment does not reduce other performance of the functionalized wood; the dimension stability is obviously improved; and the antiswelling efficient is up to 50-70%.
Description
Technical field
The present invention relates to a kind of new method of timber function improvement.Utilize the polyhydroxy-alcohol compound composite for function improvement agent treated timber or wood substrate for catalyst, low molecule hydroxymethyl resin, suppress the timber embrittlement that chemical modifying causes for modifier for toughening auxiliary agent, natural organic acids.
Background technology
Timber is the material of natural reproducible and recycle, and along with the development of national economic development and the raising of living standards of the people, people are increasing to the demand of timber.And the enforcement of wildwood protected project and domestic wildwood area coverage are relatively little, make the wood supply amount decline to a great extent.For alleviating the timber imbalance between supply and demand, large-area Industrial Plantation has been built by China.Though artificial forest has advantages such as fast growing, the density of artificial fast-growing woods timber is low, and material is soft, and physical and mechanical property is relatively poor, and expand with wet and contract with dry is prone to cause the timber distortion.These low-quality timber are short service life, apt to rot in the use, cracking and distortion etc.For the performance of improving low-quality timber to widen its range of application, to improve its utilization rate and added value, developed the function improving technology of various physics, chemistry at present.Wherein, utilize the low molecular agents of various activity that timber is carried out the chemical functional improvement and developed into ripe improving technology, successfully realized industrial applications the America and Europe.
Existing wood chemistry function improving technology comprises that mainly acetylation, furans alcohol are handled, melamine processing and 1,3-dihydroxymethyl-4, technology such as 5-dihydroxy ethylene urea (2D resin) modification.Wood acetylation is to utilize to have active acetyl group and form ester bond with hydrophily hydroxyl generation graft reaction in the wood cell wall material and is connected, reduces the hydroxyl in the wood cell wall, thereby the hygroscopicity of reduction timber, enhancing Wood Dimensional Stability.Initial acetylation is handled and is adopted pyrimidine as catalyst, and the rotten performance of the wood dimensional stability of processing and corrosion resistant obtains good improvement.The timber of furans alcohol dipping modification is called furfuryl alcoholization wood again; This technology is mainly developed by the Wood Polymer Technology Co., Ltd (Norwaegian company Wood Polymer Technologies) of Norway; And applied for multinomial international monopoly (for example, PCT/NO01/004132001.10.11, PTC/NO2003/000251/2003.7.21 and 2004-08-13PCT/NO2004/000247).Initial research is furfuryl alcohol to be replaced phenolic resins make template and inorganic composite materials as adhesive, and furfuryl alcohol is impregnated in the timber, condensation reaction takes place in wood cell wall and/or lumen then form oligomer.Under the heat and the acting in conjunction of catalyst, its end group also may with the hydroxyl generation grafting or the cross-linking reaction of wood cell wall material.It is to be modifier with the modified cyanurotriamide resin that the melmac modification is handled, and sawn timber and veneer are carried out impregnation process, can carry out the hot pressing compression to the sawn timber that floods and make highdensity compressed wood, and the veneer of handling then can be used as the dash board of glued board.The melmac modified timber; Many performances also improve; Like dimensional stability, resistance wet rate, elastic modelling quantity and MOR etc.; Main cause is that group such as methylol and wood cell wall material react in the melmac, part replaced the hydroxyl in the timber (OH), thus form the crosslinked usefulness that turns into.2D resin modified timber; Mechanism of modification also is the hydroxyl generation covalent cross-linking formation ehter bond through nitrogen methylol and wood cell wall; Improve the elastic modelling quantity and the dimensional stability of timber thus, such processing does not change wood color basically, has kept the color and luster natural attractive in appearance of timber.The research and development of 2D resin treatment technology are handled Wood Dimensional Stability, durability, anti-corrosive properties and some mechanical property and have been obtained remarkable improvement mainly in Germany, also extensive use and products such as preparation floor, glued board and door and window.
Although these chemical functional property improving technologies have given timber new characteristic and function, simultaneously also bring some negative effects, mainly show the remarkable reduction of some mechanical property (especially dynamic mechanical, like impact strength).Some hot strength of handling timber reduces more than 40%, and impact strength reduces amplitude even up to 80%.The application of timber has seriously been limited in these negative effects, the occasion that especially need carry.Compare with the untreated timber mechanical property, the bending strength of acetylation improved wood and elastic modelling quantity, impact strength have all reduced, and its treatment process is loaded down with trivial details relatively, the residual and release gradually of by-product acetic acid is arranged after the reaction, so tart flavour are dense.Timber with after the furfuryl alcohol processing becomes fragile slightly, and the wood color after the processing becomes brown, influences the natural aesthetic property of timber.Melmac is prone to wear out, hardening time is short, and in use hydrolysis can take place methylene, causes melamine itself to become fragile, and also there is the embrittlement problem in the timber of processing.The 2D resin can discharge some formaldehyde in handling the timber process, bending strength, hot strength and the impact strength of handling timber all decrease.The main cause that the mechanical property of these chemical functional improvement timber reduces can be summed up as: have the participation of acid (as catalyst) or organic acid to produce (byproduct of reaction) in (1) course of reaction; Cause especially cellulose of wood cell wall main component, catalyzing hydrolysis takes place; (2) because cross-linking reaction or the grafting of chemical reagent in wood cell wall filled, cause the timber after the modification receiving under the load condition slippage between cell membrane microfibril strand limited, timber shows as toughness decline, timber embrittlement on the macroscopic view.Therefore, the present invention is intended to keep original chemical functional and improves when giving the timber excellent properties, effectively suppresses timber impact strength reduction (timber embrittlement) this industrial technology difficult problem that chemical modification causes through correlation means.
The fragility inhibition method of chemical functional improvement timber of the present invention; Be intended to utilize polyhydroxy-alcohol as toughening auxiliary agent; Natural organic acids is a catalyst; Carry out the composite improved wood that comes with methylol compound,, thereby enlarge the range of application of improved wood with the timber embrittlement that reduces to cause in the hydroxymethyl resin modifying process.Polyhydroxy-alcohol is a toughening auxiliary agent, can react with crosslinking agent, prolongs the cross-linker molecules chain length, makes the slippage flexibly when meeting with stresses of functionalization timber molecule, plays toughness reinforcing effect.Natural organic acids uses as catalysts, be since its catalyzing hydrolysis ability relatively a little less than, can reduce the high molecular hydrolysis of timber in the processing procedure, thereby suppress the fragility of timber.And used organic acid is a natural products, has excellent environmental-protecting performance, and itself can be fixed in the timber with hydroxyl reaction in the system, and resistance leachability is good, and no environment endangers.The methylol low-molecular-weight resin then can be filled wood cell wall, and reacts with the hydroxyl of cell wall substance and polyhydroxy-alcohol, gives timber new function.
Summary of the invention
This invention utilizes the polyhydroxy-alcohol compound to handle timber or wood substrate for catalyst, low molecule hydroxymethyl resin for modifier for toughening auxiliary agent, natural organic acids; Be intended to suppress to improve this industrial problem of the serious embrittlement of timber that causes with hydroxymethyl resin merely; Thereby further improve timber hydroxymethyl resin function improving technology, the application of expanding function timber.The specific embodiments of this invention is following:
One, the prescription of modifier: select a kind of polyhydroxy-alcohol compound at least; At least select a kind of methylol compound; Two kinds of compounds add deionized water again and are made into the solution that mass fraction is 5～50% concentration by different mol ratio preparations, add the catalyst of a certain amount of percentage by solution quality; Like citric acid, magnesium chloride or zinc chloride etc., the composite function improvement reagent that makes.
Two, the dipping of timber or wood substrate: vacuum pressed equipment is used in the wood preservation processing with traditional, above-mentioned functions is improved reagent be injected in the timber.According to the difference of timber or wood substrate size, set processing parameters such as corresponding vacuum, moulding pressure and processing time.Timber or wood substrate are thin more, breadth is more little, and vacuum and the pressure then selected for use are more little, and the time is short more, otherwise then increase vacuum, pressure and dip time.
Three, the reactive polymeric of function reagent in timber or wood substrate: unseasoned lumber after will flooding or wood substrate are done in the atmospheric environment therapeutic method to keep the adverse qi flowing downward; Under the temperature of different gradients, distinguish dry special time then successively; Most of water is slowly removed; Polymerization under 100～130 ℃ of conditions at last, employed drying mode can be selected forced air drying, vacuum drying, heating using microwave, radiation heating, ultraviolet heating or Infrared Heating for use.Dry back is cooled to room temperature under atmospheric environment, promptly obtain function improvement timber or wood substrate.Dry basis of time timber or wood substrate size and decide, it is long more that thick more gas was done with the dry time, otherwise short more.
The chemical substance that the present invention selected for use is following:
(1) the polyhydroxy-alcohol compound selects for use.Used polyhydroxy-alcohol compound can be ethylene glycol, polyethylene glycol, 1; 2-propane diols, 1, ammediol, butanediol, 1,2-pentanediol, 1; 2-hexylene glycol, glycerine, sorbierite, 1; 4-butanediol, 1,6-hexylene glycol, 1,12-dodecanol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, three contract four propane diols, two glycerine, triglycerin.Such alcohol should be water-soluble, the high boiling polyhydroxy-alcohol that contains 2～18 C atoms, in prescription, can only add a kind ofly, also can multiplely make up.
(2) methylol compound selects for use.At least select a kind of low-molecular-weight resin that contains methylol, can be derivative, 2D resin and the derivative thereof etc. of melamine.Wherein, the methylol low-molecular-weight resin can be one or more combinations.
(3) catalyst selects for use.At least select a kind of catalyst, perhaps multiple composite.The optional MgCl of catalyst
2.6H
2O, plain (the main component MgCl in Kangding
2), citric acid, zinc chloride, ammonium persulfate, phenodiazine dimethyl bisacrylamide, Loprazolam, phthalic anhydride and p-methyl benzenesulfonic acid.Especially citric acid, MgCl
2.6H
2O, plain (the main component MgCl in Kangding
2), zinc chloride.
The present invention utilizes the polyhydroxy-alcohol compound compound as chemical modification reagent as flexibilizer and low molecule hydroxymethyl resin, and timber or wood based materials are carried out the chemical functional improvement, and prepared timber or wood substrate range of application are mainly following:
Indoor floor; Furniture; Timber window; Timber; Building component (signboard; Baffle plate; Threshold; Support); Handle of a knife; The wood toy; Kitchen utensils; Sales counter; Ship parts (fence; The floor; Deck assembly; The floor, deck; Furniture; Accessory) outdoor apparatus; The arena; Outdoor pavement; Machine part (conveyer belt batten; Saw guides; Saw and planer table top); Bridge railings; Freeway infrastructure (guard rail rod; Guardrail board; Signal lever; Lamp stand); The veneer overlay material; Wood-based plate; Reorganization wood; Timber.
The present invention utilize the polyhydroxy-alcohol compound as toughening auxiliary agent, natural organic acids for catalyst and the methylol oligomer resin is compound as chemical modification reagent timber or wood based materials is carried out the chemical functional improvement; By two kinds of functional groups in natural loose structure of timber and cell membrane; Polymerization reaction take place forms ehter bond; Crosslinking agent itself can react with the alcohol of introducing; Thereby prolonged the strand length of crosslinking agent, thereby helped the timber molecule slippage flexibly when meeting with stresses after crosslinked, played toughness reinforcing effect.
Utilize the functionalization timber of the present invention's technology preparation, its impact strength significantly improves.Compare with untreated timber, the impact strength decreased 75% of the functionalization timber of toughness reinforcing processing not, and the impact strength of toughness reinforcing processing timber only descends 35%.Simultaneously, toughness reinforcing processing does not reduce other performance of functionalization timber, and its dimensionally stable property improvement effect is obvious, and anti-breathing rate reaches 50～70%.The carrying drug ratio of prepared timber is 5～80%, because the injection of chemical reagent, the global density of timber improves.
The specific embodiment
Technical scheme of the present invention is not limited to the following specific embodiment of giving an example, and also comprises the particular combination between each specific embodiment.
Basic implementation method: utilize the polyhydroxy-alcohol compound to be function improvement agent treated timber or wood substrate for modifier is composite for catalyst, low molecule hydroxymethyl resin for toughening auxiliary agent, natural organic acids; Suppress the method that chemical modifying causes the timber embrittlement, basic skills is following:
One, the prescription of modifier: select a kind of polyhydroxy-alcohol compound at least; At least select a kind of methylol compound; (polyhydroxy-alcohol: mol ratio methylol compound) is 0.2～3: 1 to two kinds of compounds, adds deionized water and is made into the solution that mass fraction is 5～50% concentration, presses 0.1～5% of solution quality and adds a certain amount of functionalization catalyst; Like citric acid, magnesium chloride or zinc chloride etc., be re-dubbed function improvement reagent.
Two, the dipping of timber or wood substrate: according to timber or the different size of wood substrate, use vacuum pressed equipment, setting under corresponding vacuum, moulding pressure and the time parameter thereof with traditional wood preservation; Above-mentioned functions is improved reagent be injected in the timber, according to the timber or the wood substrate of different-thickness, vacuum is-0.02 to-0.1MPa; Vacuum time is 30min～12h; Moulding pressure is 0.3～1MPa, and be 30min-12h pressing time, and thin more vacuum of selecting for use of timber or wood substrate and pressure are more little; Time is short more, otherwise then increases vacuum, pressure and dip time.
Three, the reactive polymeric of function reagent in timber or wood substrate: unseasoned lumber after will flooding or wood substrate were done 1～3 day in the atmospheric environment therapeutic method to keep the adverse qi flowing downward; Then successively 40; 60; 80 ℃ of respectively dry down 2～6h, at last again through 100～130 ℃ of following polymerization 24h, employed drying mode can be selected forced air drying, vacuum drying, heating using microwave, radiation heating, ultraviolet heating or Infrared Heating for use.24h is cooled off in dry back under atmospheric environment, promptly be prepared into timber or wood substrate after the modification.Dry basis of time timber or wood substrate thickness and decide, it is long more that thick more gas was done with the dry time, otherwise short more.
The specific embodiment one: material modified selects for use.The modification object that this embodiment is selected for use can be: the timber of various different quality grades and various wood substrate such as medium density fibre board (MDF), particieboard or glued board.
The specific embodiment two: the selecting for use of polyhydroxy-alcohol compound.According to basic implementation method first, what this embodiment was different with it is that polyhydroxy-alcohol selects for use in this embodiment; The polyhydroxy-alcohol compound that can further select for use is ethylene glycol, polyethylene glycol, 1; 2-propane diols, 1, ammediol, butanediol, 1,2-pentanediol, 1; 2-hexylene glycol, glycerine, sorbierite, 1; One or more combinations in four propane diols, two glycerine, the triglycerin of contracting of 4-butanediol, 1,6-hexylene glycol, 1,12-dodecanol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, three.The carbon atom number of used polyhydroxy-alcohol is 2～18, and water soluble, boiling point are more than 130 ℃.
The specific embodiment three: contain the use of methylol compound.According to basic implementation method first, what this embodiment was different with it is, the selecting for use of methylol compound in this embodiment, and that can further select for use contains derivative, 2D resin and the derivative thereof that methylol compound is a melamine.Especially select the 2D resin for use, wherein, methylol compound can be one or more combinations.
The specific embodiment four: selection of catalysts.According to basic implementation method first, what this embodiment was different with it is, the further clear and definite selection of catalyst type, and catalyst system therefor can be the single or multiple composite catalysis system that forms, like citric acid, MgCl
2.6H
2O, plain (the main component MgCl in Kangding
2), zinc chloride, ammonium persulfate, phenodiazine dimethyl bisacrylamide, Loprazolam, phthalic anhydride and p-methyl benzenesulfonic acid.
The specific embodiment five: preparation functionalization timber is used for physical property evaluation.Different is with the specific embodiment one to four, the processing parameter that this embodiment is selected to confirm as an example, specifically like table one:
Table one: three kinds of different mol ratio compounds are mixed with variable concentrations formulations prepared from solutions functionalization timber
Preparation functionalization timber is used for physical property evaluation.Utilize ethylene glycol to handle timber for catalyst, 2D resin for modifier is re-dubbed function improvement reagent for toughening auxiliary agent, MgCl2.6H2O, prepared functional timber is used for the assessment of physical property, and concrete grammar is following:
One, the prescription of modifier: select ethylene glycol and 2D resin for use, the mol ratio of two kinds of compounds (2D portions of resin ethylene glycol) is 1: 0.2,1: 1 and 1: 3, and adding deionized water, to be made into mass fraction be 10%, 20% and the solution of 30% 3 kind of concentration.Press 1%, 2% and 3% of solution quality and add a certain amount of MgCl
2.6H
2The O catalyst mixes the back and stirs 10min.With the deionized water impregnated timber as blank control group, and through 30%2D resin and 2%MgCl
2.6H
2The timber test specimen of O solution-treated is as reference group.
Two, the dipping of timber or wood substrate: select the poplar wooden unit of 20mm*20mm*20mm (be followed successively by tangential, radially and vertically), each group poplar wooden unit is 20, prepares 11 groups.Elder generation's vacuum, vacuum is-0.06MPa, vacuum time 0.5h is forced into 0.6MPa again, pressing time 2h, through this dipping process, the modifier that above-mentioned prescription is prepared is injected in the timber.
Three, the dry polymerization of timber or wood substrate: unseasoned lumber after will flooding or wood substrate were done 2 days in the atmospheric environment therapeutic method to keep the adverse qi flowing downward; Then successively at 40 ℃ of following dry 4h, 60 ℃ of following dry 4h and 80 ℃ of following dry 4h; Again through 120 ℃ of polymerisation 24h, select the air dry oven heating for use at last.Under atmospheric environment, cool off 24h after the polymerization, promptly be prepared into the functionalization timber after the modification.
The specific embodiment six: preparation functionalization timber is used for impact flexibility and tensile strength parallel to grain test.Different is with the specific embodiment one to four; The embodiment of selecting in this embodiment to confirm is as case study; Different is that the size of timber test specimen is different in this embodiment, has selected polyhydroxy-alcohol compound and three kinds of catalyst of three kinds of chemical structures for use with the specific embodiment five; Use catalyst concn also inconsistent, and modifier concentration constant (30%).Its research approach such as following table two:
Table two: select for use different polyhydroxy-alcohols and different catalysts to prepare functionalization timber
Concrete method of modifying is following:
One, the polyhydroxy-alcohol selected for use of this specific embodiment has ethylene glycol, 1,2-propane diols and 1, and three kinds of ammediols, every kind of alcohol is composite with the 2D resin respectively, and the mol ratio of two kinds of compounds is 1: 1, adds deionized water and is made into the solution that mass fraction is 30% concentration.The catalyst of selecting for use also has three kinds, is respectively citric acid, MgCl
2.6H
2O and zinc chloride, and 2%, 3% and 2% adding respectively of pressing liquid quality fraction respectively mix the back and stir 10min.
Two, the dipping of timber or wood substrate: select to be of a size of the poplar of 20mm*20mm*300mm (be followed successively by tangential, radially and vertically), each group test specimen is 20, totally ten one groups.Other is identical with the description in the specific embodiment five (two, three).
The specific embodiment seven: the physical property test result of improved wood.The functionalization wooden unit that this specific embodiment will make according to the specific embodiment five is to relevant physical property evaluation, like carrying drug ratio (WPG), moisture content (MC), anti-breathing rate (ASE) and turnover rate (L).
The computing formula of carrying drug ratio is:
WPG=(M
2-M
1)/M
1* 100% formula (1)
In the formula: M
1The oven dry weight of-untreated samples;
M
2The oven dry weight of-processing sample.
The computing formula of anti-breathing rate is:
ASE=(S
0-S
1)/S
0* 100% formula (2)
In the formula: S
0Cross-sectional area expansion (contraction) rate of-untreated samples;
S
1Cross-sectional area expansion (contraction) rate of-processing sample.
The computing formula of turnover rate is:
L=(M
2-M
3)/(M
2-M
1) * 100% formula (3)
In the formula: M
1The oven dry weight of-untreated samples;
M
2The oven dry weight of-processing sample;
M
3Oven dry weight behind the-processing sample water logging bubble.
Moisture content is operated and is calculated according to GB 1931-1991 " Method for determination of the moisture content of wood ".
Following table three is the result of each item physical property test:
Table three: three kinds of different mol ratio compounds are mixed with carrying drug ratio, moisture content, anti-breathing rate and the turnover rate result of the test of variable concentrations formulations prepared from solutions functionalization timber
Result in the table three shows; Moisture content and reagent turnover rate that three kinds of different mol ratio compounds are mixed with variable concentrations formulations prepared from solutions functionalization timber reduce along with the increase of carrying drug ratio; Anti-harmomegathus rate is obviously improved; Can under identical 2D resin concentration, add the test specimen (E that toughening auxiliary agent is handled up to more than 70%
1, E
2And E
3) on each item detection index, all will improve than reference group (B).
The specific embodiment eight: impact flexibility and tensile strength parallel to grain result of the test.The functionalization timber that this specific embodiment makes according to the specific embodiment six; Sample dimensions is 20mm*20mm*300mm (is followed successively by tangential, radially and vertically); Be used for the test of impact ductility test and tensile strength parallel to grain, impact flexibility is by the impact strength evaluation.
The experimental technique of impact flexibility is operated according to current national standard GB1940-1991 " timber impact flexibility experimental technique ", and its computing formula is:
At first, the energy that calculation testing piece absorbs, formula is:
Q=W (h
1-h
2)=Wl (cos θ
2-cos θ
1) (J) formula (4)
In the formula: Q is the energy (J) that test specimen absorbs; W is the pendulum quality; 1 is the distance (m) of pendulum fulcrum to striking point; h
1And θ
1For the starting altitude (m) of pendulum with lay out the lift angle degree; h
2And θ
2For destroying height and the angle that pendulum reaches.
Secondly, the impact flexibility of timber is obtained by following formula:
R=1000Q/bh (kJ/m
2) formula (5)
In the formula: R is the impact strength (kJ/m of test specimen
2), Q is the energy (J) that test specimen absorbs; B, h are the width and the height (mm) of test specimen.
The tensile strength parallel to grain experimental technique can be operated according to current national standard GB1938-1991 " timber tensile strength parallel to grain experimental technique ", and computing formula is:
σ
W=P
Max/ tb (M) formula (6)
In the formula: σ
WBe test specimen cis-position tensile strength; P
MaxBe maximum load (N); T, b are the thickness and the width (mm) of test specimen.
Following table four is the experimental result of impact flexibility and tensile strength parallel to grain:
Table four: select for use different polyhydroxy-alcohols and different catalysts to prepare functionalization timber
Impact flexibility and tensile strength perpendicular to grain experimental result
Visible by the result in the table four, compare with untreated timber, reduce by 74.58% without the impact strength of the functionalization timber (reference group) of toughness reinforcing processing, and the functionalization timber impact strength of toughness reinforcing processing only reduces by 35.40%; Reference group timber tensile strength parallel to grain reduces by 51.88%, and the functionalization timber of toughness reinforcing processing only reduces by 23.81%.Show that thus toughness reinforcing processing method of the present invention can effectively suppress the embrittlement of chemistry functional timber.
Claims (7)
1. the fragility method of inhibitioning of chemical functional improvement timber is characterized in that utilizing the polyhydroxy-alcohol compound as chemical modification reagent timber or wood substrate to be carried out chemical functional improvement, the timber embrittlement that reduction causes owing to chemical modification for catalyst and hydroxymethyl resin oligomer are composite as toughening auxiliary agent, natural organic acids; Guarantee to strengthen the dimensional stability and the rotten ability of corrosion resistant of timber or wood substrate simultaneously, concrete steps are following: one, the preparation of modifier: select a kind of polyhydroxy-alcohol compound at least and select a kind of methylol compound at least; (polyhydroxy-alcohol: mol ratio methylol compound) is 0.2～3: 1 to two kinds of compounds, adds deionized water and is made into the solution that mass fraction is 5～50% concentration, presses 0.1～5% of liquid quality fraction and adds a certain amount of catalyst; Be re-dubbed function improvement reagent, two, the dipping of timber or wood substrate: use vacuum pressed equipment with traditional wood preservation, according to timber or the different size of wood substrate; Under vacuum, moulding pressure and the time parameter thereof set, above-mentioned functions is improved reagent be injected in the timber, according to the timber or the wood substrate of different-thickness; Vacuum is-0.02 to-0.1MPa; Vacuum time is 30min～12h, and moulding pressure is 0.3～1MPa, and be 30min～12h pressing time; Thin more vacuum of selecting for use of timber or wood substrate and pressure are more little; Time is short more, otherwise then increases vacuum, pressure and dip time, and three, the reactive polymeric of function reagent in timber or wood substrate: unseasoned lumber after will flooding or wood substrate were done 1～3 day in the atmospheric environment therapeutic method to keep the adverse qi flowing downward; Then successively 40; 60,80 ℃ of respectively dry down 2～6h are at last again through 100～130 ℃ of following polymerization 24h; Employed drying mode can be selected forced air drying, vacuum drying, heating using microwave, radiation heating, ultraviolet heating or Infrared Heating for use; 24h is cooled off in dry back under atmospheric environment, promptly be prepared into timber or wood substrate after the modification, dry basis of time timber or wood substrate thickness and decide; Thick more gas is done with the dry time long more, otherwise short more.
2. the fragility inhibition method of chemical functional improvement timber according to claim 1 is characterized in that described timber is the timber of various grades, and wood substrate is medium density fibre board (MDF), particieboard or glued board.
3. the fragility inhibition method of chemical functional improvement timber according to claim 1; It is characterized in that the polyhydroxy-alcohol compound described in claim 1 first step can be ethylene glycol, polyethylene glycol, 1; 2-propane diols, 1; Ammediol, butanediol, 1,2-pentanediol, 1,2-hexylene glycol, glycerine, sorbierite, 1; 4-butanediol, 1; One or more combinations in four propane diols, two glycerine, the triglycerin of contracting of 6-hexylene glycol, 1,12-dodecanol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, three, this polyhydroxy-alcohol can comprise that carbon atom is that 2 to 18 water soluble and boiling point are at the polyhydroxy-alcohol more than 130 ℃.
4. the fragility inhibition method of chemical functional improvement timber according to claim 1; It is characterized in that the methylol compound described in claim 1 first step can be the derivative of melamine, 1; 3-dihydroxymethyl-4; 5-dihydroxy ethylene urea (2D resin) and derivative thereof, wherein, methylol compound can be one or more combinations.
5. the fragility inhibition method of chemical functional improvement timber according to claim 1 is characterized in that the catalyst described in claim 1 first is citric acid, MgCl
2.6H
2O, plain (the main component MgCl in Kangding
2), in zinc chloride, ammonium persulfate, phenodiazine dimethyl bisacrylamide, Loprazolam, phthalic anhydride and the p-methyl benzenesulfonic acid one or more.
6. the fragility method of inhibitioning of chemical functional according to claim 1 improvement timber, it is characterized in that using timber or the combination of wood substrate and modifier after this method processing is following six kinds:
(1)W-(D)
X-W
(2)W-(E)
Y-W
(3)W-[D-(E)
x-D]
Y-W
(4)W-[E-(D)
X-E]
Y-W
(5)W-(D)
X-(E)
Y-W
(6)W-[(D-E)
Z]
M-W
Wherein, in combination (1)～(6):
W is the main component of timber or wood substrate, fine cellulose, hemicellulose and lignin,
D is one or more combinations in the methylol compound described in the claim 4,
E is one or more combinations, the especially ethylene glycol, 1 in the many methylols alcoholic compound described in the claim 3,2-propane diols, 1.3-propane diols and polyethylene glycol,
X is in the methylol compound according to claim 4, methylol (CH
2-OH) and HO-CH
2-under the condition of the catalyst described in the claim 5, become ether or ester according to the described drying condition catalysis of third part in the claim 1 polycondensation, promptly-CH
2-O-CH
2-or-C (O)-O-C-, its degree of polymerization is 10～10000, Y is in many methylols alcoholic compound according to claim 3, alcoholic extract hydroxyl group [(CH
2) n-OH] and-(CH
2) n-OH under the condition of the catalyst described in the claim 5, become ether or ester according to the described polymerizing condition catalysis of third part in the claim 1 polycondensation, promptly-(CH
2) n-O-(CH
2) degree of polymerization of n-, the scope of Y is 10～10000, the scope of n is 2～18,
Z is according to described polyhydroxy-alcohol of difference and methylol in the claim 3,4, (CH
2) n-OH and HO-CH
2-under the condition of the catalyst described in the claim 5, become ether according to the described polymerizing condition catalysis of third part in the claim 1 polycondensation, promptly-(CH
2) n-O-CH
2-the degree of polymerization, can be 10～10000,
M be according in the combination described in the claim 6 (6)-(CH
2) n-O-CH
2-replace the degree of polymerization that combines, can be 1～5000.
7. the fragility inhibition method of chemical functional improvement timber according to claim 1 is characterized in that the functionalization timber or the wood substrate that prepare can middlely in the following areas use:
Indoor floor; Furniture; Timber window; Timber; Building component (signboard; Baffle plate; Threshold; Support); Handle of a knife; The wood toy; Kitchen utensils; Sales counter; Ship parts (fence; The floor; Deck assembly; The floor, deck; Furniture; Accessory) outdoor apparatus; The arena; Outdoor pavement; Machine part (conveyer belt batten; Saw guides; Saw and planer table top); Bridge railings; Freeway infrastructure (guard rail rod; Guardrail board; Signal lever; Lamp stand); The veneer overlay material; Wood-based plate; Reorganization wood; Timber.
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| CN103433988A (en) * | 2013-08-27 | 2013-12-11 | 东北林业大学 | Method for performing functional improvement on wood by using polybasic carboxylic acid |
| CN103659968A (en) * | 2013-12-05 | 2014-03-26 | 东北林业大学 | Method for preparing preservative-treated wood by using environmental protection low molecular weight organic pharmaceutical agent |
| CN103659968B (en) * | 2013-12-05 | 2016-01-20 | 东北林业大学 | A kind of method utilizing the organic medicament of environmental protection low molecule to prepare preserving timber |
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| CN107283566A (en) * | 2017-04-24 | 2017-10-24 | 中国林业科学研究院木材工业研究所 | Musical instrument fingerboard wood materials and preparation method thereof and its acoustic function body maceration extract |
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| CN107599092B (en) * | 2017-08-30 | 2020-12-01 | 广东省林业科学研究院 | Nitrogen hydroxymethyl ethylene urea resin modifier and application thereof |
| CN108481473A (en) * | 2018-05-25 | 2018-09-04 | 南京林业大学 | A kind of manufacturing method of high added value laminated veneer lumber |
| CN108481473B (en) * | 2018-05-25 | 2023-11-21 | 南京林业大学 | Manufacturing method of laminated veneer lumber with high added value |
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