CN103358372B - A kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood - Google Patents
A kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood Download PDFInfo
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- CN103358372B CN103358372B CN201310299782.9A CN201310299782A CN103358372B CN 103358372 B CN103358372 B CN 103358372B CN 201310299782 A CN201310299782 A CN 201310299782A CN 103358372 B CN103358372 B CN 103358372B
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Abstract
A kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood, first by O-Phenylene Diamine acidifying, secondly the O-Phenylene Diamine after acidifying and HPAA solution are mixed to get modification liquid, then by abundant for modification liquid impreg material, simultaneously in confined conditions by heating and thermal insulation make the O-Phenylene Diamine after acidifying and HPAA in wood reaction in－situ generate phosphorous benzimidizole derivatives, then keep air tight condition, cooling, ageing; Finally wash, dry, obtain at the phosphorous benzimidizole derivatives properties-correcting agent of timber in-situ preparation.Synthesis technique of the present invention is simple, pollution-free, utilizes the hydroxyl in the hydroxyl of phosphorous benzimidizole derivatives and timber to form hydrogen bond etc. and acts on and be combined on timber; Phosphorous benzimidizole derivatives adheres to and is filled in timber duct, improves the density of timber, hydrophobicity, water tolerance, ultimate compression strength and wear resistance, and makes timber have good dimensional stability and fire-retardant fireproof characteristic.
Description
Technical field
The present invention relates to Wood property improvement technical field, be specially a kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood.
Background technology
Timber is traditional building and furniture upholstery, carries out modification to timber, gives timber better waterproof, hot subject that dimensional stabilizing, the performance such as wear-resisting, corrosion-resistant, fire-retardant are wood processing field always.At present, the synthesis condition of a lot of organic fire-retardant is harsh, and unfriendly to environment, and cost is higher, and resistance leachability is poor, can play waterproof simultaneously, insect protected, fire-retardant properties-correcting agent are few especially.
In traditional Wooden modifying process, the properties-correcting agent molecular weight used is comparatively large or particle is large, is difficult to immerse in timber; Or impregnate efficiency to improve, have to adopt properties-correcting agent soluble in water or fire retardant, not resistance to drip washing, the easily moisture absorption is easily caused to return frost, as: the main component of CN201010214843.3 " processing method of modifying synthetic resin impregnated wood " is resol; CN201210123456.8 " the wear-resisting integral treatment method of the fire-retardant Hardening of a kind of fast growing wood " adopt properties-correcting agent to be the aqueous suspension of nano-aluminum hydroxide and silane coupling agent; CN200910076762.9 " Wooden modifying composition and its preparation method and application " Main Components is phosphoric acid, itrogenous organic substance, borate, Secondary ammonium phosphate, ammonium chloride; The saturated aqueous solution that CN94111437.6 " Wood flame-retarded technology " fire retardant is phosphoric acid hydrogen two ammonium, the saturated aqueous solution of boric acid, alum or phosphoric acid add ammoniacal liquor, ammonium phosphate, primary ammonium phosphate, ammonium hydrogen phosphate; In CN201210194615.3 " a kind of method based on situ aggregation method modification fast growing wood ", first synthetic urea-formaldehyde resin modification liquid, and then Precondensed UreaFormaldehyde Resin modification liquid is immersed polymerizing curable in timber.
The above-mentioned properties-correcting agent used for Wooden modifying, in intrusion timber soluble in water, timber is improved, but properties-correcting agent also easily flows out after to timber improvement, can not solidify in wood, the water absorbability of timber is caused to reduce dimensional instability, frost is returned in not resistance to drip washing, the easily moisture absorption, affects the flame retardant resistance of timber.Therefore, how to improve the density of timber, hydrophobicity, water tolerance, ultimate compression strength and wear resistance, and make timber have good dimensional stability and fire-retardant fireproof characteristic; The properties-correcting agent that adds in wood is simultaneously both water insoluble, is also insoluble to organic solvent, and having the feature 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 a kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood, to solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
A kind of phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood, first by O-Phenylene Diamine acidifying, secondly the O-Phenylene Diamine after acidifying and phosphono oxyacetic acid (HPAA) solution are mixed to get modification liquid, then by abundant for modification liquid impreg material, simultaneously in confined conditions by heating and thermal insulation make the O-Phenylene Diamine after acidifying and HPAA in wood reaction in－situ generate phosphorous benzimidizole derivatives, then keep air tight condition, cooling, ageing; Finally take out reacted wood materials, washing, dry, obtain at the phosphorous benzimidizole derivatives properties-correcting agent of timber in-situ preparation.In Wood modifier formation reaction process, utilize chemical reaction scheme 1, in timber duct or surface in situ generate one be insoluble in water, also the phosphorous benzimidizole derivatives of organic solvent is insoluble in, wood surface is adhering closely to after hydroxyl in the semipolar hydroxyl of phosphorous benzimidizole derivatives and timber forms hydrogen bond or other chemical bondings, the water absorbability that the hydrophobicity that has nonpolar phenyl ring effectively improves timber reduces dimensional stability, and phosphorous benzimidizole derivatives is a kind of containing N, the compound of P ignition-proof element, give timber good flame retardant resistance simultaneously, its reaction formula is as follows:
Comprise the steps:
Secondly (1) first by O-Phenylene Diamine acidifying, be that 0.8:1 ~ 1.5:1 is mixed to get modification liquid by the O-Phenylene Diamine after acidifying and HPAA solution according to mol ratio;
(2) by step (1) gained modification liquid, abundant impreg material;
(3) O-Phenylene Diamine after promoting acidifying by heating and thermal insulation in confined conditions and HPAA in wood reaction in－situ generate phosphorous benzimidizole derivatives;
(4) after step (3) reaction terminates, air tight condition is kept, cooling, ageing;
(5) take out through step (4) reacted wood materials, washing, dry.
In the present invention, O-Phenylene Diamine souring soln acidity described in step (1) is the phosphoric acid solution of 0.8 ~ 1.0mol/L or the hydrochloric acid soln of 1.0 ~ 4.0mol/L; HPAA solution is the aqueous solution of HPAA, and concentration is 30 ~ 50%.
In the present invention, described in step (2), wood materials is log, thin plate, wood chip, wood powder, fiberboard, paper making raw material.
In the present invention, dipping described in step (2) is normal pressure dipping or vacuum-impregnating by pressure.
In the present invention, temperature of reaction described in step (3) is 120 DEG C ~ 150 DEG C, 0.5 ~ 4 hour insulation reaction time.
In the present invention, after the reaction of step (3) described in step (4) terminates, the cooling and aging time is greater than 24 hours.
In the present invention, washing described in step (5) is deionized water or pure water.
In the present invention, dry described in step (5): solid wood sample, according to drying schedule, is put into dry kiln and carried out air seasoning; Wood powder sample in 105 ~ 120 DEG C of baking ovens dry 6 ~ 12 hours.
In the present invention, O-Phenylene Diamine after acidifying and HPAA are soluble in water, thus than being easier to immerse in timber, and O-Phenylene Diamine and the HPAA phosphorous benzimidizole derivatives that generates of reaction in－situ in wood, both water insoluble, also be insoluble to organic solvent, therefore phosphorous benzimidizole derivatives properties-correcting agent has the advantages that Yi Jinnan goes out, and is adapted to add do properties-correcting agent in wood; O-Phenylene Diamine and HPAA in wood reaction in－situ generate the semipolar hydroxyl of phosphorous benzimidizole derivatives and timber in hydroxyl form hydrogen bond or other chemical bondings after be adhering closely to wood surface, phosphorous benzimidizole derivatives adheres to and is filled in timber duct, effectively improve the density of timber, hydrophobicity, water tolerance, ultimate compression strength and wear resistance, nonpolar phenyl ring has the water absorbability reduction dimensional stability that hydrophobicity improves timber; Phosphorous benzimidizole derivatives is a kind of compound containing N, P ignition-proof element simultaneously, gives the flame retardant resistance that timber is good.The method that this timber situ synthesizes phosphorous benzimidizole derivatives properties-correcting agent has that synthesis technique is simple, advantages of environment protection.
beneficial effect
In the present invention, phosphorous benzimidizole derivatives synthesizes in aqueous environments, pollution-free, technique is simple; Generated in-situ phosphorous benzimidizole derivatives insoluble in water and organic solvent in wood, has effect that is water-fastness, corrosion-resistant, fire-retardant, desinsection, can be used for the modification of solid wood board side and the wood materials such as glued board, fiberboard; The phosphorous benzimidizole derivatives simultaneously generated at wood surface or duct covers the hydroxyl of wood surface, reduces the ability of hydroxyl adsorption moisture in timber, water is reduced modified wood wetting capacity, thus enhances the waterproof of timber, corrosion resistant performance; Generated in-situ phosphorous benzimidizole derivatives integrates N, P element in wood, can play the effect of N-P cooperative flame retardant when running into fire, effectively suppresses spreading of flame.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Case study on implementation 1
(1) 55 parts of O-Phenylene Diamines and 100 parts of 2mol/L phosphoric acid are uniformly 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 of 100 parts of acidifyings is added in 200 parts of 50%HPAA solution, stir 20min and mix, obtain modification liquid;
(4) be that the poplar plate side of 2000mm × 200mm × 20mm loads in vacuum high-pressure immersion can by specification; Open vacuum pump evacuation, maintaining tank internal pressure is 0.01 ~ 0.02MPa.30min; Open liquid flowing valve by modification liquid suction immersion can, make liquid level cover poplar plate side completely, add 1.5 ~ 1.8MPa pressure impregnation 1 ~ 2 h;
(5) open draining valve, modification hydraulic pressure is returned reservoir, give over to after adjustment proportioning and use next time;
(6) open drain tap, after removal pressure, poplar plate side is loaded in confined reaction groove, be heated to 140 DEG C of reaction 4 ~ 8 h;
(7) after step (6) reaction terminates, poplar plate side is taken out from reactive tank, naturally cooling, display more than 24 hours;
(8) poplar plate side is put into dry kiln, carry out air seasoning according to drying schedule.
In the present embodiment, the poplar plate side density after process reaches 0.69g/cm
3, color and luster is without noticeable change, and anti-breathing rate (ASE) index can reach 68%, and the wet rate MEE of resistance is 64%, ultimate compression strength improves 0.7 times, and wear loss declines 60%, and acetylene flame does not burn through for 4 minutes, from flame from putting out, evenly heat rate of release reduces by 51.2%, and total heat release reduces 46.3%.
Case study on implementation 2
(1) 55 parts of O-Phenylene Diamines and 100 parts of 2mol/L phosphoric acid are uniformly 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 of 100 parts of acidifyings is added in 200 parts of 50%HPAA solution, stir 20min and mix, obtain modification liquid;
(4) be that 2500mm × 400mm × 3mm poplar thin plate loads in vacuum high-pressure immersion can by specification; Open vacuum pump evacuation, maintaining tank internal pressure is 0.01 ~ 0.02MPa.30min; Open liquid flowing valve by modification liquid suction immersion can, make liquid level cover poplar plate side completely, add 1.5 ~ 1.8MPa pressure impregnation, 20 ~ 40min;
(5) open draining valve, modification hydraulic pressure is returned reservoir, give over to after adjustment proportioning and use next time;
(6) open drain tap, after removal pressure, poplar thin plate is loaded in confined reaction groove, be heated to 140 DEG C of reaction 2 ~ 3 h;
(7) after step (6) reaction terminates, poplar plate side is taken out from reactive tank, naturally cooling, display more than 24 hours;
(8) poplar thin plate is put into dry kiln, carry out air seasoning according to drying schedule.
In the present embodiment, the poplar thin plate applying glue after process is hot pressed into plate, and compared with untreated glued board, ultimate compression strength improves about 0.78 times, and ASE is that 60%, MEE is about 49%.Evenly heat rate of release reduces by 57%, and total heat release reduces 50.3%.
Case study on implementation 3
(1) adopt 120g30%HPAA aqueous solution normal temperature and pressure dipping 80g Poplar Powder 1 hour, obtain mixture;
(2) adopt the 1mol/L hydrochloric acid of 400ml by after the acidifying of 0.1mol O-Phenylene Diamine, then add the mixture in step (1), stir;
(3) be warming up to 130 ~ 140 DEG C, stir, react 3 hours, be cooled to below room temperature, hold over night, filter, adopt solution washing, detect without chlorion to washings;
(4) step (3) gained Modified Poplar powder is placed in baking oven, 105 DEG C ~ 120 DEG C dryings 1 ~ 2 hour;
(5) by dried Poplar Powder in step (4), after applying glue, in thermocompressor, plate is hot pressed into.
In the present embodiment, processing Poplar Powder plate density is 0.82g/cm
3, ultimate compression strength reaches 50MPa, and bending strength increases 20%.Taper calorimetric experimental result shows: under 50kW yield of radiation, and after process, Poplar Powder plate reduces nearly 60% than the evenly heat rate of release of untreated Poplar Powder plate, and total heat release reduces 64.7%, and residue of combustion adds 2.7 times.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets 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.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. a phosphorous benzimidizole derivatives properties-correcting agent in-situ preparation method in wood, is characterized in that, comprise the steps:
Secondly (1) first by O-Phenylene Diamine phosphoric acid solution or hydrochloric acid soln acidifying, be that 0.8:1 ~ 1.5:1 is mixed to get modification liquid by the O-Phenylene Diamine after acidifying and the HPAA aqueous solution according to mol ratio;
(2) by step (1) gained modification liquid, abundant impreg material;
(3) O-Phenylene Diamine after promoting acidifying by heating and thermal insulation in confined conditions and the HPAA aqueous solution in wood reaction in－situ generate phosphorous benzimidizole derivatives; Described temperature of reaction is 120 DEG C ~ 150 DEG C;
(4) after step (3) reaction terminates, air tight condition is kept, cooling, ageing more than 24 hours;
(5) take out through step (4) reacted wood materials, washing, dry.
2. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, it is characterized in that, be the phosphoric acid solution of 0.8 ~ 1.0mol/L or the hydrochloric acid soln of 1.0 ~ 4.0mol/L by the solution of O-Phenylene Diamine acidifying in step (1); HPAA aqueous solution mass concentration is 30 ~ 50%.
3. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, it is characterized in that, wood materials described in step (2) is log, wooden thin plate, wood chip, wood powder, fiberboard.
4. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, is characterized in that, dipping described in step (2) is normal pressure dipping or vacuum-impregnating by pressure.
5. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, is characterized in that, 0.5 ~ 4 hour insulation reaction time in described step (3).
6. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, is characterized in that, washing described in step (5) is deionized water or pure water.
7. a kind of phosphorous benzimidizole derivatives properties-correcting agent according to claim 1 in-situ preparation method in wood, is characterized in that, dry described in step (5): solid wood sample, according to drying schedule, is put into dry kiln and carried out air seasoning; Wood powder sample in 105 ~ 120 DEG C of baking ovens dry 6 ~ 12 hours.
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567277A (en) * | 1981-09-28 | 1986-01-28 | Basf Aktiengesellschaft | Salts of 2-(methoxy-carbonylamino)-benzimidazole |
| CN1305347A (en) * | 1998-04-17 | 2001-07-25 | 马特史密斯控股有限公司 | Biocidal composition containing phosphite ions |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567277A (en) * | 1981-09-28 | 1986-01-28 | Basf Aktiengesellschaft | Salts of 2-(methoxy-carbonylamino)-benzimidazole |
| CN1305347A (en) * | 1998-04-17 | 2001-07-25 | 马特史密斯控股有限公司 | Biocidal composition containing phosphite ions |
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Granted publication date: 20151021 Termination date: 20160717 |