CN102699966A - Method for modifying fast-growing wood based on in-situ polymerization method - Google Patents
Method for modifying fast-growing wood based on in-situ polymerization method Download PDFInfo
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- CN102699966A CN102699966A CN2012101946153A CN201210194615A CN102699966A CN 102699966 A CN102699966 A CN 102699966A CN 2012101946153 A CN2012101946153 A CN 2012101946153A CN 201210194615 A CN201210194615 A CN 201210194615A CN 102699966 A CN102699966 A CN 102699966A
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Abstract
The invention discloses a method for modifying fast-growing wood based on an in-situ polymerization method. The method comprises the steps as follows: (1) synthesizing a wood modifying solution; (2) dipping the fast-growing wood; and (3) carrying out in-situ polymerization reaction on active groups in the wood modifying solution and wood fiber cell functional groups. According to the method, chemical wood modifying and drying processes are integrated; the process is simple and the price is low; and the performance such as density, hardness, size stability and hydrophobicity of the fast-growing wood and the like is effectively improved.
Description
Technical field
The present invention relates to a kind of method of fast growing wood chemical modification, particularly relate to the method for situ aggregation method modification fast growing wood log, belong to the field of wood processing treatment technology.
Background technology
Timber is a kind of porous material; A lot of spaces are arranged; Like the microcapillary in lumen, space between cells, pit and the cell membrane, the entering that becomes moisture or liquid provides passage and place, also for the circulation of Wood modifier and infiltration necessary condition is provided.On the other hand, in the three big compositions of timber, cellulose contain a large amount of hydroxyls (OH) and ehter bond (O-), contain a large amount of primary alconol base (CH in the hemicellulose
2OH), secondary alcohol groups (CHOH), carboxyl (COOH), methoxyl group (OCH
3) and acetyl group (OCCH
3), contain methoxyl group (OCH in the lignin
3), (OH), (C=O), these groups all are the groups with certain reactivity to carbonyl to hydroxyl, are easy to take place cross-linking polymerization under certain condition.The application of home position polymerization reaction in timber is the micropore shape structure of having utilized timber, the reaction active groups of wood surface.At first that the Wood modifier impregnated timber is inner; In timber drying; The effect of heat causes macerate and the effect of timber generation cross-linked polymeric, reaction beginning, monomer pre-polymerization, performed polymer polymerization down; After performed polymer polymerization size progressively increases, with the timber polymerization crosslinking and disperse in inside, wood cell chamber and the space between cells.Through the in-situ polymerization modified timber, not only improved physical and mechanical property, improved dimensional stability, the more important thing is that the Wood modifier resistance leachability is strong owing to the home position polymerization reaction effect.
CN 101954662A has reported the method for utilizing the combined modified timber of organic monomer inflation grafting cell membrane and polymerization tytosis chamber; Method has mainly adopted organic acid anhydride inflation grafting and organic mode of gathering the monomer polymerization filling; The organic matter improved wood that this method adopts; There are serious secondary pollution and organic recycling problem; The method of the vacuum pressed dipping that secondly adopts in the method need be to the timber and the dried of impregnation process, and above-mentioned two aspects have greatly limited the suitability for industrialized production of this method.
CN 1890071A has reported a kind of Wood treatment method that comprises the in-situ polymerization under the electromagnetic radiation; Adopted organic monomer in the method; And the reactant of at least two glycidyl functional groups' reactant and at least two primary amine or secondary amine-NH functional group in this monomer, and the timber behind the dipping is exposed to wavelength 1-10
-3In the electromagnetic radiation of rice, power is 300-1000 watt, and this method has not only been used organic matter, also has energy consumption greatly, also is unfavorable for suitability for industrialized production.
CN 102127216A has reported a kind of preparation method who contains the polymerizable Wood modifier of long ether chain of polarity and both-end thiazolinyl; Adopted the organic monomer and the polyethylene glycol of purifying to mix, added certain toluene, triethylamine and hydrogen chloride solution etc., under the condition of nitrogen protection, reacted; Product after overwinding steams is dissolved in the ethyl acetate; Pass through the organic facies analysis once more, revolve steaming once more, above-mentioned preparation method is loaded down with trivial details not easy to operate; And have certain toxicant to use, there is this secondary pollution problem equally.
WO 01/5305 has reported the method through vinyl monomer in-situ polymerization and crosslinking Treatment timber; Comprise under the existence of divinyl crosslinking agent and at least a oil or a kind of wax; At least but in the radical polymerization of mixture of the monofunctional vinyl monomer that causes of different initator; The innovation wood of this processing method preparation has dense residual monomer, and human body is had certain injury.
In addition, the situ aggregation method patent that changes lignocellulosic as: US 3,765; 934 have reported the wooden cellulosic method of employing maleic anhydride situ aggregation method modification, and US 4,148; 949 have reported the method that adopts vinyl monomer situ aggregation method raising lignocellulosic reaction rate; US 6,063, and 883 have reported that situ aggregation method reduces the method for the hardness of wood lastingly.
The key factor of Wooden modifying is the mode of impregnation process and cured, the endurance issues of the cost of improved wood, especially modifier; Present technique adopts the fresh log of pulsed impregnating by pressure mode direct impregnation on the one hand, has reduced the cost of pre-dried, has adopted compound Wood modifier on the other hand; Not only do not contain organic matter, preparation technology is simple, the most important thing is; Home position polymerization reaction occurs in the timber drying after the impregnation process; Active reactive group generation cross-linked polymeric effect in compound Wood modifier and the timber at the inner space network that forms of timber, has not only improved the individual character performance of timber; Wood modifier is difficult for running off after the modification, has realized the purpose of lasting modification.
Summary of the invention
It is simple, cheap that one of the object of the invention has provided a kind of technology, effectively improves the method for performances such as fast growing wood density, hardness, dimensional stability, hydrophobicity.
Two of the object of the invention is that said method is to realize through situ aggregation method modification fast growing wood.
Three of the object of the invention is that above-mentioned home position polymerization reaction is in timber drying, to accomplish.
Four of the object of the invention is that said method has realized that fast growing wood chemical modification and the drying of wood are integrated.
Above-mentioned purpose of the present invention is to realize through following technical scheme:
(1) Wooden modifying liquid: participating in the reactive activity reactive group in the Wooden modifying liquid is amino (NH
2) and hydroxyl (OH);
(2) fresh fast growing wood dipping; Dipping gets into the wood element Wooden modifying liquid from fast growing wood log termination through pulsed impregnating by pressure machine;
(3) home position polymerization reaction takes place: the log after the impregnation process is processed into the sheet material of all size according to demand; Under hot conditions, above-mentioned dipping sheet material is carried out high temperature drying and handle, home position polymerization reaction takes place in active group in the Wooden modifying liquid and wood element functional group.
In step (1), Wooden modifying liquid is according to the synthetic preparation of certain ratio by formaldehyde, urea, hexa, ammoniacal liquor, NaOH, polyethylene glycol.
In step (1), Wooden modifying liquid synthetic as follows: in the aqueous solution of urea of 40% concentration, add the hexa that accounts for the qualitative 6-10% of urea solid content, mix, the pH value of controlling solution is 6.4-6.5; Be that 37% formalin joins in the agitated reactor according to certain ratio with a certain amount of concentration, start stirring; After the reaction beginning, need lower the temperature to above-mentioned mixed liquor with mixture of ice and water, the temperature that guarantees entire reaction stirred 3 hours in 20-40 ℃ with this understanding, after question response finishes, in product, added a certain amount of polyethylene glycol.
In step (1), the formaldehyde of Wooden modifying liquid, the mol ratio of urea are 1.0-1.3:1;
In step (1), the synthetic temperature of Wooden modifying liquid is controlled at 20-40 ° of C;
In step (1), possesses this reactive activity of participation group (NH in the Wooden modifying liquid
2) and (molecular weight distribution of compound OH) is between 400-800.
In step (1), the content of polyethylene glycol is the 10%-30% that volume accounts for Wooden modifying liquid in the Wooden modifying liquid;
In step (1), the molecular weight of polyethylene glycol preferably 400 or 600 in the Wooden modifying liquid.
In step (2), the fast growing wood moisture content that is used to flood is more than 50%, and the impregnation method of employing is the pulsed impregnating by pressure, and pickup calculates according to the porosity of log, and impregnation pressure is 0.3-0.8MPa, and dip time often is 25-60min.
In step (3), the preferred specification of the sheet material that log is processed into after the impregnation process is that thickness is 20mm, 30mm or 50mm.
In step (3), the sheet material after the sawing processing is packed in the dry kiln, and sheet material is placed to separate and is parallel to each other; Make drying medium vertically flow along sheet material; In addition, place dividing plate between the sheet material, help to heat sheet material on the one hand; Sheet material is heated evenly, helps the evaporation of moisture in the sheet material on the other hand.
In step (3), the dry drying medium temperature of sheet material is warmed up to 130 ℃ gradually from room temperature, and the time is 4-8 days.
In step (3), home position polymerization reaction occurs in the amino (NH in the Wooden modifying liquid
2), hydroxyl (OH) and the hydroxyl in the wood structure (OH).
In step (3), home position polymerization reaction has formed nitrogenous ester bond and ehter bond in wood element.
In step (3), home position polymerization reaction takes place between lumber fibre component and Wooden modifying liquid, has formed space network, has realized the persistence of lumber functionality improvement.
The invention has the advantages that:
(1) the present invention has combined the natural quality of timber---a kind of natural porous macromolecular material, for home position polymerization reaction provides necessary condition;
(2) molecular weight distribution of the active reaction composition in the Wooden modifying liquid is between 400-800, helps being penetrated in wood cell wall, the lumen and in the space between cells;
(3) taked pulsed impregnating by pressure machine to fresh fast growing wood log impregnation process;
(4) home position polymerization reaction is accompanied by in the timber drying and takes place, and has realized the integrated of wood chemistry modification and dry run;
(5) between lumber fibre component and Wooden modifying liquid because home position polymerization reaction, formed ester bond and ehter bond, prevented the leachability of Wooden modifying liquid effectively.
Description of drawings
Fig. 1 is the sketch map of situ aggregation method modification fast growing wood; Wherein, (
representes hydrone to the Wooden modifying liquid of Fig. 1 (A) expression preparation;
representes peg molecule,
expression contain amino active reaction body); Fig. 1 (B) representes untreated fresh timber cross section; Timber cross section after Fig. 1 (C) expression impregnation process; Timber cross section after the home position polymerization reaction takes place in Fig. 1 (D) expression.
Fig. 2 is the schematic diagram of home position polymerization reaction.
The specific embodiment
Can further be expressly understood the present invention through specific embodiment of the present invention given below, but following embodiment is not to qualification of the present invention.
Embodiment 1:
(1) in the aqueous solution of urea of 40% concentration, add 10% the hexa account for urea solid content quality, mix, the pH value of regulator solution is 6.5; With concentration be 37% formalin according to joining in the agitated reactor with the certain ratio of urea 1.0:1, start stirring; After the reaction beginning, need lower the temperature to above-mentioned mixed liquor with mixture of ice and water, the temperature that guarantees mixed liquor stirred 3 hours between 20-40 ℃ with this understanding, after question response finishes, in product, added 10% the polyethylene glycol that accounts for that modified liquid amasss;
(2) impregnation method that adopts is the fresh poplar of pulsed impregnating by pressure, and the moisture content of poplar is 75%, and the specification of the sheet material that the log sawing is processed into after the impregnation process is that thickness is 30mm;
(3) sheet material after the impregnation process is put into the processing of high temperature drying kiln inner drying, and the drying medium temperature is raised to 130 ℃ gradually from room temperature, 6 days drying times;
(4) in the dry run, home position polymerization reaction occurs in the amino (NH in the Wooden modifying liquid
2), hydroxyl (OH) and the hydroxyl in the wood element (OH), generated nitrogenous ester bond and ehter bond, formed space network.
Embodiment 2:
(1) in the aqueous solution of urea of 40% concentration, add the hexa that accounts for urea solid content 6%, mix, the pH value of regulator solution is 6.4; Be that 37% formalin joins in the agitated reactor according to the ratio with urea 1.3:1 with concentration, start stirring; After the reaction beginning, need lower the temperature to above-mentioned mixed liquor with mixture of ice and water, the temperature that guarantees mixed liquor stirred 3 hours in 20-40 ℃ of scope with this understanding, after question response finishes, in product, added the polyethylene glycol that accounts for modified liquid long-pending 30%;
(2) impregnation method that adopts is a pulsed impregnating by pressure Eucalyptus, and the moisture content of Eucalyptus is 55%, and the sheet material that log is processed into after the impregnation process is that gauge thickness is 50mm;
(3) sheet material after the impregnation process is put into the processing of high temperature drying kiln inner drying, and the drying medium temperature is raised to 130 ℃ gradually from room temperature, and be 4 days drying time;
(4) in the dry run, home position polymerization reaction occurs in the amino (NH in the Wooden modifying liquid
2), hydroxyl (OH) and the hydroxyl in the wood structure (OH), generated nitrogenous ester bond and ehter bond, formed space network.
Embodiment 3:
(1) in the aqueous solution of urea of 40% concentration, add the hexa that accounts for urea solid content 8%, mix, the pH value of regulator solution is 6.4; Be that 37% formalin joins in the agitated reactor according to the ratio with urea 1.2:1 with concentration, start stirring; After the reaction beginning, need lower the temperature to above-mentioned mixed liquor with mixture of ice and water, the temperature that guarantees mixed liquor stirred 3 hours in 20-40 ℃ of scope with this understanding, after question response finishes, in product, added the polyethylene glycol that accounts for modified liquid long-pending 20%;
(2) impregnation method that adopts is a pulsed impregnating by pressure Eucalyptus, and the moisture content of Eucalyptus is 85%, and the sheet material that log is processed into after the impregnation process is that gauge thickness is 20mm;
(3) sheet material after the impregnation process is put into the processing of high temperature drying kiln inner drying, and the drying medium temperature is raised to 130 ℃ gradually from room temperature, and be 8 days drying time;
(4) in the dry run, home position polymerization reaction occurs in the amino (NH in the Wooden modifying liquid
2), hydroxyl (OH) and the hydroxyl in the wood structure (OH), generated nitrogenous ester bond and ehter bond, formed space network.
Claims (7)
1. method based on situ aggregation method modification fast growing wood; It is characterized in that; 1. this method comprises the steps:: synthetic wood modification liquid: in the aqueous solution of urea of 40% concentration, add the hexa that accounts for urea solid content 6-10%; Mix, the pH value of control solution is 6.4-6.5; Be 37% formalin with concentration according to formaldehyde and urea mol ratio be that the ratio of 1.0-1.3:1 joins in the agitated reactor; Start stirring, mixing time is 3 hours, synthesizes the temperature of entire reaction simultaneously with mixture of ice and water control fast growing wood modification liquid; Temperature is between 20 ℃-40 ℃; After treating that above-mentioned reaction finishes, in reactant liquor, add polyethylene glycol, and the polyethylene glycol that adds accounts for the long-pending 10-30% of above-mentioned Wooden modifying liquid; 2.: dipping gets into the wood element Wooden modifying liquid 1. synthetic through step from fast growing wood log termination through pulsed impregnating by pressure machine; 3.: the fast growing wood after the impregnation process can be processed into the sheet material of various sizes according to demand, obtains under hot conditions, carrying out high temperature drying behind the sheet material of required specification and handles, and makes the active group amino group (NH in the Wooden modifying liquid
2), oh group (OH) with the lumber fibre structure in hydroxyl (OH) take place to form the nitrogenous ester bond and the home position polymerization reaction of diether linkage structure.
2. according to the described method of claim 1, it is characterized in that possessing this reactive activity of participation group (NH in the 1. middle Wooden modifying liquid of step
2) and (molecular weight distribution of composition OH) is between 400-800.
3. according to the described method of claim 1, it is characterized in that the polyethylene glycol that step adds in 1. is molecular weight 400 or 600 polyethylene glycol preferably.
4. according to the described method of claim 1, it is characterized in that the fast growing wood of step in 2. is that moisture content is at the fast growing wood more than 50%.
5. according to the described method of claim 1; It is characterized in that when step was utilized pulsed impregnating by pressure machine dipping fast growing wood in 2., pickup was to calculate according to the porosity of fast growing wood log to draw; Impregnation pressure is 0.3-0.8MPa, and dip time is 25-60min.
6. according to the described method of claim 1, it is characterized in that the gauge of the fast growing wood processing after the 3. middle impregnation process of step is 20mm, 30mm or 50mm preferably.
7. according to the said method of claim 1; It is characterized in that the high temperature drying of step in 3. handled through following method and accomplished: pack the timber that obtains required specification in the dry kiln into the separate and placement that is parallel to each other of timber; Drying medium is vertically flowed along sheet material; Also need place dividing plate in addition between the timber, the drying medium temperature of timber is warmed up to 130 ° of C gradually from room temperature, and dry required time is 4-8 days.
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| CN102699966B CN102699966B (en) | 2014-04-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105751335A (en) * | 2016-03-10 | 2016-07-13 | 内蒙古农业大学 | Novel modified wood and preparation method thereof |
| CN106217536A (en) * | 2016-08-04 | 2016-12-14 | 南京博俊新材料有限公司 | A kind of cross-linking type Wood modifier |
| CN108080237A (en) * | 2017-11-28 | 2018-05-29 | 太和县鎏禧木业有限公司 | A kind of Surface finishing processes of elm furniture |
Citations (4)
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|---|---|---|---|---|
| EP0531551A1 (en) * | 1991-04-04 | 1993-03-17 | Az Company | Lumber processing agent, processed lumber, and method of processing lumber |
| JP2001288444A (en) * | 2000-04-04 | 2001-10-16 | Showa Highpolymer Co Ltd | Impregnating and adhesive bonding resin composition |
| CN101549508A (en) * | 2009-03-20 | 2009-10-07 | 北京林业大学 | Technical method for lumber functionality improvement |
| CN101618559A (en) * | 2009-04-22 | 2010-01-06 | 宁波高新区木圣科技有限公司 | Medicated liquid pressuring and injecting equipment for log modification |
-
2012
- 2012-06-14 CN CN201210194615.3A patent/CN102699966B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0531551A1 (en) * | 1991-04-04 | 1993-03-17 | Az Company | Lumber processing agent, processed lumber, and method of processing lumber |
| JP2001288444A (en) * | 2000-04-04 | 2001-10-16 | Showa Highpolymer Co Ltd | Impregnating and adhesive bonding resin composition |
| CN101549508A (en) * | 2009-03-20 | 2009-10-07 | 北京林业大学 | Technical method for lumber functionality improvement |
| CN101618559A (en) * | 2009-04-22 | 2010-01-06 | 宁波高新区木圣科技有限公司 | Medicated liquid pressuring and injecting equipment for log modification |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105751335A (en) * | 2016-03-10 | 2016-07-13 | 内蒙古农业大学 | Novel modified wood and preparation method thereof |
| CN106217536A (en) * | 2016-08-04 | 2016-12-14 | 南京博俊新材料有限公司 | A kind of cross-linking type Wood modifier |
| CN106217536B (en) * | 2016-08-04 | 2018-01-16 | 南京博俊新材料有限公司 | A kind of cross-linking type Wood modifier |
| CN108080237A (en) * | 2017-11-28 | 2018-05-29 | 太和县鎏禧木业有限公司 | A kind of Surface finishing processes of elm furniture |
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| CN102699966B (en) | 2014-04-30 |
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