CN103358372A - In-situ generation method of phosphorus-containing benzimidazole derivative modifier in timber - Google Patents
In-situ generation method of phosphorus-containing benzimidazole derivative modifier in timber Download PDFInfo
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- CN103358372A CN103358372A CN 201310299782 CN201310299782A CN103358372A CN 103358372 A CN103358372 A CN 103358372A CN 201310299782 CN201310299782 CN 201310299782 CN 201310299782 A CN201310299782 A CN 201310299782A CN 103358372 A CN103358372 A CN 103358372A
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- phenylenediamine
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Abstract
An in-situ generation method of a phosphorus-containing benzimidazole derivative modifier in timber comprises: firstly acidifying o-phenylenediamine; secondly mixing the acidified o-phenylenediamine and a HPAA solution to obtain a modification treatment fluid; then fully dipping the timber in the modification treatment fluid, and at the same time under an airtight condition heating and keeping warm to generate a phosphorus-containing benzimidazole derivative via an in-situ reaction of the acidified o-phenylenediamine and HPAA in the timber; then keeping the airtight condition, cooling, aging; and finally washing and drying to obtain the in-situ generated phosphorus-containing benzimidazole derivative modifier in the timber. The method is simple in synthetic technology and free in pollution; by using interactions such as hydrogen-bond interaction formed between the hydroxyl group of the phosphorus-containing benzimidazole derivative and the hydroxyl group in the timber, the phosphorus-containing benzimidazole derivative is bonded with the timber; and because the phosphorus-containing benzimidazole derivative is adhered to and filled in timber channels, the timber is improved in density, hydrophobic property, water resistance, compressive strength and wear resistance, and the timber has good dimension stability and characteristics of flame retardation and fire resistance.
Description
Technical field
The present invention relates to the Wood property improvement technical field, be specially the original position generation method of a kind of phosphorous benzimidizole derivatives modifier in timber.
Background technology
Timber is traditional building and furniture upholstery, and timber is carried out modification, gives the better waterproof of timber, dimensionally stable, the performance such as wear-resisting, corrosion-resistant, fire-retardant is the hot subject of wood processing field always.At present, the synthesis condition of a lot of organic fire-retardants is harsh, and unfriendly to environment, and cost is higher, and resistance leachability is poor, can play simultaneously waterproof, insect protected, fire-retardant modifier is few especially.
During traditional Wooden modifying was processed, employed modifier molecular weight was large or particle is large, is difficult to immerse in the timber; Perhaps impregnate efficient in order to improve, have to adopt modifier soluble in water or fire retardant, easily cause not anti-drip washing, the easy moisture absorption to return frost, as: the main component of CN201010214843.3 " process of modifying synthetic resin impregnated wood " is phenolic resins; CN201210123456.8 " the wear-resisting integral treatment method of the fire-retardant Hardening of a kind of fast growing wood " modifier that adopts is the aqueous suspension of nano-aluminum hydroxide and silane coupler; CN200910076762.9 " Wooden modifying composition and its preparation method and application " Main Components is phosphoric acid, itrogenous organic substance, borate, diammonium hydrogen phosphate, ammonium chloride; CN94111437.6 " Wood flame-retarded technology " fire retardant is the saturated aqueous solution of phosphoric acid hydrogen two ammoniums, boric acid, alum or the saturated aqueous solution that phosphoric acid adds ammoniacal liquor, ammonium phosphate, ammonium dihydrogen phosphate (ADP), ammonium hydrogen phosphate; In CN201210194615.3 " a kind of method based on situ aggregation method modification fast growing wood ", synthetic urea-formaldehyde resin modification liquid at first, and then the pollopas modification liquid immersed polymerizing curable in the timber.
Above-mentioned for the employed modifier of Wooden modifying, in the intrusion timber soluble in water timber is improved, but modifier also flows out after to the timber improvement easily, can not in timber, solidify, cause the hygroscopicity of timber to reduce dimensional instability, not anti-drip washing, the easy moisture absorption are returned frost, affect the anti-flammability of timber.Therefore, how to improve density, hydrophobicity, resistance to water, compression strength and the wearability of timber, and make timber have good dimensional stability and fire-retardant fireproof characteristic; The modifier that adds in timber is simultaneously both water insoluble, also is insoluble to organic solvent, and having the characteristics that Yi Jinnan goes out is those skilled in the art's problem demanding prompt solutions.
Summary of the invention
Technical problem solved by the invention is to provide the original position generation method of a kind of phosphorous benzimidizole derivatives modifier in timber, to solve the shortcoming in the above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
The original position generation method of a kind of phosphorous benzimidizole derivatives modifier in timber, at first with the o-phenylenediamine acidifying, secondly the o-phenylenediamine after the acidifying and phosphono glycolic acid (HPAA) solution are mixed to get modification liquid, then with the abundant impreg material of modification liquid, make o-phenylenediamine and HPAA after acidifying generate phosphorous benzimidizole derivatives in the reaction of timber situ by heat tracing in confined conditions simultaneously, then keep airtight condition, cooling, ageing; Take out at last reacted wood materials, washing, drying namely gets in the timber original position and generates phosphorous benzimidizole derivatives modifier.In Wood modifier reaction of formation process, utilize chemical reaction scheme 1, in the timber duct or surface in situ generate and a kind ofly to be insoluble in water, also to be insoluble in the phosphorous benzimidizole derivatives of organic solvent, close attachment was at wood surface after hydroxyl in the semipolar hydroxyl of phosphorous benzimidizole derivatives and the timber formed hydrogen bond or other chemical bondings, the hygroscopicity that nonpolar phenyl ring has hydrophobicity Effective Raise timber reduces dimensional stability, and phosphorous benzimidizole derivatives is the compound of a kind of N of containing, P ignition-proof element, gives simultaneously timber good anti-flammability; Its reaction equation is as follows:
Comprise the steps:
(1) at first with the o-phenylenediamine acidifying, be that 0.8:1～1.5:1 is mixed to get modification liquid with the o-phenylenediamine after the acidifying and HPAA solution according to mol ratio secondly;
(2) with step (1) gained modification liquid, abundant impreg material;
(3) promote o-phenylenediamine and HPAA after the acidifying to generate phosphorous benzimidizole derivatives in the reaction of timber situ by heat tracing in confined conditions;
(4) after step (3) reaction finishes, keep airtight condition, cooling, ageing;
(5) take out through the reacted wood materials of step (4) washing, drying.
In the present invention, o-phenylenediamine souring soln acidity described in the step (1) is the phosphoric acid solution of 0.8～1.0mol/L or the hydrochloric acid solution of 1.0～4.0mol/L; HPAA solution is the aqueous solution of HPAA, and concentration is 30～50%.
In the present invention, wood materials is log, thin plate, wood chip, wood powder, fiberboard, paper making raw material described in the step (2).
In the present invention, dipping described in the step (2) is normal pressure dipping or vacuum-impregnating by pressure.
In the present invention, reaction temperature described in the step (3) is 120 ℃～150 ℃, 0.5～4 hour insulation reaction time.
In the present invention, after the reaction of step (3) described in the step (4) finished, the cooling and aging time was greater than 24 hours.
In the present invention, washing described in the step (5) is deionized water or pure water washing.
In the present invention, dry described in the step (5): the solid wood sample is put into dry kiln and is carried out aeration-drying according to drying schedule; Wood powder sample in 105～120 ℃ of baking ovens dry 6～12 hours.
In the present invention, o-phenylenediamine after the acidifying and HPAA are soluble in water, thereby than being easier to immerse in the timber, and the phosphorous benzimidizole derivatives that o-phenylenediamine and HPAA generate in the reaction of timber situ, both water insoluble, also be insoluble to organic solvent, therefore phosphorous benzimidizole derivatives modifier has the advantages that Yi Jinnan goes out, and is adapted to be added on and does modifier in the timber; O-phenylenediamine and HPAA behind the semipolar hydroxyl of phosphorous benzimidizole derivatives that timber situ reaction generates and the formation hydrogen bond of the hydroxyl in the timber or other chemical bondings close attachment at wood surface, phosphorous benzimidizole derivatives adheres to and is filled in the timber duct, Effective Raise the density of timber, hydrophobicity, resistance to water, compression strength and wearability, nonpolar phenyl ring has the hygroscopicity that hydrophobicity improves timber and reduces dimensional stability; Phosphorous benzimidizole derivatives is the compound of a kind of N of containing, P ignition-proof element simultaneously, gives timber good anti-flammability.The method of the synthetic phosphorous benzimidizole derivatives modifier of this timber situ has that synthesis technique is simple, advantages of environment protection.
Beneficial effect
Phosphorous benzimidizole derivatives is synthetic, pollution-free in aqueous environments among the present invention, technique is simple; Phosphorous benzimidizole derivatives insoluble in water and organic solvent in that the timber situ generates have effect water-fastness, corrosion-resistant, fire-retardant, desinsection, can be used for the modification of the wood materials such as solid wood board side and glued board, fiberboard; The phosphorous benzimidizole derivatives that generates in wood surface or duct simultaneously covers the hydroxyl of wood surface, has weakened the ability of hydroxyl adsorption moisture in the timber, so that water reduces the improved wood wetting capacity, thereby has strengthened the waterproof of timber, corrosion resistant performance; The phosphorous benzimidizole derivatives that generates at the timber situ integrates N, P element, can play the effect of N-P cooperative flame retardant when running into fire, the spreading of establishment flame.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Case study on implementation 1
(1) 55 parts of o-phenylenediamines and 100 parts of 2mol/L phosphoric acid are mixed, obtain the o-phenylenediamine solution of acidifying;
(2) HPAA and water are mixed with 50%HPAA solution by 1:1 quality proportioning;
(3) o-phenylenediamine solution with 100 parts of acidifyings adds in 200 parts of 50%HPAA solution, stirs 20min and mixes, and gets modification liquid;
(4) be to pack in the vacuum high-pressure immersion can in the poplar plate side of 2000mm * 200mm * 20mm specification; The unlatching vavuum pump vacuumizes, and keeping the tank internal pressure is 0.01～0.02MPa.30min; Open liquid flowing valve with in the modification liquid suction immersion can, make liquid level cover poplar plate side fully, add 1.5～1.8MPa pressure impregnation, 1～2 h;
(5) open draining valve, modification hydraulic pressure is returned reservoir, give over to after the adjustment proportioning and use next time;
(6) open drain tap, behind the removal pressure, packed in the confined reaction groove in poplar plate side, be heated to 140 ℃ of reaction 4～8 h;
(7) after step (6) reaction finishes, poplar plate side is taken out from reactive tank, cooling was displayed more than 24 hours naturally;
(8) poplar plate side is put into dry kiln, carry out aeration-drying according to drying schedule.
In the present embodiment, the poplar plate side density after the processing reaches 0.69g/cm
3, color and luster is without marked change, and anti-breathing rate (ASE) index can reach 68%, and the wet rate MEE of resistance is 64%, compression strength improves 0.7 times, and abrasion loss descends 60%, and acetylene flame did not burn through in 4 minutes, from putting out, the evenly heat rate of release reduces by 51.2% from flame, and total heat release reduces 46.3%.
Case study on implementation 2
(1) 55 parts of o-phenylenediamines and 100 parts of 2mol/L phosphoric acid are mixed, obtain the o-phenylenediamine solution of acidifying;
(2) HPAA and water are mixed with 50%HPAA solution by 1:1 quality proportioning;
(3) o-phenylenediamine solution with 100 parts of acidifyings adds in 200 parts of 50%HPAA solution, stirs 20min and mixes, and gets modification liquid;
(4) be that 2500mm * 400mm * 3mm poplar thin plate is packed in the vacuum high-pressure immersion can with specification; The unlatching vavuum pump vacuumizes, and keeping the tank internal pressure is 0.01～0.02MPa.30min; Open liquid flowing valve with in the modification liquid suction immersion can, make liquid level cover poplar plate side fully, add 1.5～1.8MPa pressure impregnation, 20～40min;
(5) open draining valve, modification hydraulic pressure is returned reservoir, give over to after the adjustment proportioning and use next time;
(6) open drain tap, behind the removal pressure, the poplar thin plate is packed in the confined reaction groove, be heated to 140 ℃ of reaction 2～3 h;
(7) after step (6) reaction finishes, poplar plate side is taken out from reactive tank, cooling was displayed more than 24 hours naturally;
(8) the poplar thin plate is put into dry kiln, carry out aeration-drying according to drying schedule.
In the present embodiment, the poplar thin plate applying glue after the processing is hot pressed into plate, compares with the glued board that is untreated, and compression strength improves about 0.78 times, and ASE is that 60%, MEE is about 49%.The evenly heat rate of release reduces by 57%, and total heat release reduces 50.3%.
Case study on implementation 3
(1) adopts 120g30%HPAA aqueous solution normal temperature and pressure dipping 80g Poplar Powder 1 hour, get mixture;
(2) the 1mol/L hydrochloric acid that adopts 400ml with the acidifying of 0.1mol o-phenylenediamine after, then add the mixture in the step (1), stir;
(3) be warming up to 130～140 ℃, stir, reacted 3 hours, be cooled to below the room temperature, hold over night is filtered, and adopts solution washing, detects without chlorion to cleaning solution;
(4) step (3) gained Modified Poplar powder is placed in the baking oven, 105 ℃～120 ℃ dryings 1～2 hour;
(5) with dried Poplar Powder in the step (4), in hot press, be hot pressed into plate after the applying glue.
In the present embodiment, processing Poplar Powder plate density is 0.82g/cm
3, compression strength reaches 50MPa, and bending strength increases 20%.Taper calorimetric experimental result shows: under the 50kW radiation intensity, after processing the Poplar Powder plate reduce than the evenly heat rate of release of the Poplar Powder plate that is untreated nearly 60%, total heat release minimizing 64.7%, residue of combustion has increased by 2.7 times.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. the original position generation method of a phosphorous benzimidizole derivatives modifier in timber is characterized in that, comprises the steps:
(1) at first with the o-phenylenediamine acidifying, be that 0.8:1～1.5:1 is mixed to get modification liquid with the o-phenylenediamine after the acidifying and HPAA solution according to mol ratio secondly;
(2) with step (1) gained modification liquid, abundant impreg material;
(3) promote o-phenylenediamine and HPAA after the acidifying to generate phosphorous benzimidizole derivatives in the reaction of timber situ by heat tracing in confined conditions;
(4) after step (3) reaction finishes, keep airtight condition, cooling, ageing;
(5) take out through the reacted wood materials of step (4) washing, drying.
2. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber, it is characterized in that o-phenylenediamine souring soln acidity described in the step (1) is the phosphoric acid solution of 0.8～1.0mol/L or the hydrochloric acid solution of 1.0～4.0mol/L; HPAA solution is the aqueous solution of HPAA, and concentration is 30～50%.
3. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that wood materials is log, thin plate, wood chip, wood powder, fiberboard, paper making raw material described in the step (2).
4. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that, dipping described in the step (2) is normal pressure dipping or vacuum-impregnating by pressure.
5. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that reaction temperature described in the step (3) is 120 ℃～150 ℃, 0.5～4 hour insulation reaction time.
6. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that, after the reaction of step (3) described in the step (4) finished, the cooling and aging time was greater than 24 hours.
7. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that, washing described in the step (5) is deionized water or pure water washing.
8. the original position generation method of a kind of phosphorous benzimidizole derivatives modifier according to claim 1 in timber is characterized in that, dry described in the step (5): the solid wood sample is put into dry kiln and carried out aeration-drying according to drying schedule; Wood powder sample in 105～120 ℃ of baking ovens dry 6～12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493469A (en) * | 2018-03-13 | 2018-09-04 | 中国科学院上海有机化学研究所 | A kind of cross-linking type high temperature proton exchange film and preparation method thereof |
| CN112493247A (en) * | 2020-08-31 | 2021-03-16 | 北农（海利）涿州种衣剂有限公司 | Dry powder seed coating agent and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3138575A1 (en) * | 1981-09-28 | 1983-04-07 | Basf Ag, 6700 Ludwigshafen | FUNGICIDE |
| KR20010052260A (en) * | 1998-04-17 | 2001-06-25 | 메이나드, 니겔 폴 | A biocidal composition containing phosphite ions |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493469A (en) * | 2018-03-13 | 2018-09-04 | 中国科学院上海有机化学研究所 | A kind of cross-linking type high temperature proton exchange film and preparation method thereof |
| CN108493469B (en) * | 2018-03-13 | 2020-08-07 | 中国科学院上海有机化学研究所 | Cross-linked high-temperature proton exchange membrane and preparation method thereof |
| CN112493247A (en) * | 2020-08-31 | 2021-03-16 | 北农（海利）涿州种衣剂有限公司 | Dry powder seed coating agent and production process thereof |
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Granted publication date: 20151021 Termination date: 20160717 |