CN102975250A - Wood modifier and preparation method thereof - Google Patents
Wood modifier and preparation method thereof Download PDFInfo
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- CN102975250A CN102975250A CN2012104798685A CN201210479868A CN102975250A CN 102975250 A CN102975250 A CN 102975250A CN 2012104798685 A CN2012104798685 A CN 2012104798685A CN 201210479868 A CN201210479868 A CN 201210479868A CN 102975250 A CN102975250 A CN 102975250A
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Abstract
The invention relates to a wood modifier and a preparation method thereof. The wood modifier comprises the following raw materials by weight parts: 50-180 parts of phosphoric acid, 30-60 parts of urea, 0.2-0.5 part of catalyst and 1-6 parts of butanetetracarboxylic acid. According to the wood modifier provided by the invention, the butanetetracarboxylic acid is primarily applied to the field of wood treatment and is matched with other components, reasonable proportion is performed, and a good synergy effect is achieved; and compared with the prior art, the wood modifier is excellent in drainage prevention performance, contributes to wood size stability, is excellent in flame-retardant efficiency, simple in preparation method and low in cost.
Description
Technical field
The present invention relates to chemical reagent field used on the timber-work, particularly, relate to a kind of Wood modifier, and its preparation method.
Background technology
Timber and goods thereof are widely used in interior decoration, Furniture manufacture, building construction and the extraneous adornment, these materials belong to combustible material, very easily cause fire, and easily expand with wet and contract with dry, dimensional stability are relatively poor, how to improve the anti-flammability of material and the problem that dimensional stability has become whole world extensive concern.
At present, the most popular method that prevents timber and goods breaking out of fire thereof is to use fire retardant in these materials, these fire retardants are mostly based on compounds such as phosphorous, nitrogen, boron, aluminium and halogens, inorganic combustion inhibitor owing to have good flame resistance, do not produce toxic gas (except the halogen flame), do not separate out, the characteristics such as non-volatile, cheap, wide material sources, security height are used widely.
Open day be to disclose a kind of fire-proof flame-retarded agent in April 5, publication number in 2000 Chinese patent application that is CN1249325A, this fire retardant is mixed by urea, phosphoric acid, borax, boric acid etc., is applicable to the fire-retardant of the combustibles such as cotton, chemical fibre, paper, timber.
Open day be to disclose a kind of phosphor nitrogen composite combustion inhibitor in July 26, publication number in 2006 Chinese patent application that is CN1807552A, this fire retardant carries out adding behind the chemical reaction nertralizer such as ammonia by urea and phosphoric acid again and carries out neutralization reaction and make, and is applicable to the fire-retardant of the combustibles such as textile and timber-work.
The patent No. provides fire retardant of a kind of formaldehyde effect of dissolving for possessing of Wood and artificial board and preparation method thereof for the Chinese patent of ZL200710122243.2.
Although disclosed fire retardant has simple, the low cost and other advantages of manufacture method in the above-mentioned document, its resistance leachability is all relatively poor, to the not contribution of dimensional stability of timber.
Summary of the invention
The purpose of this invention is to provide a kind of Wood modifier and preparation method thereof.This Wood modifier dimensionally stable, resistance leachability is good.
Wood modifier provided by the invention comprises the raw material of following weight portion: 50 ~ 180 parts of phosphoric acid, 30 ~ 60 parts in urea, 1 ~ 6 part of 0.2 ~ 0.5 part of catalyst and BTCA.
Wood modifier provided by the invention preferably, comprises the raw material of following weight portion: 50 ~ 150 parts of phosphoric acid, 32 ~ 54 parts in urea, 2 ~ 6 parts of 0.25 ~ 0.48 part of catalyst and BTCAs.
Wherein, described catalyst is: stannic chloride, copper sulphate, sodium chloride, iron chloride, aluminum sulfate, boric acid and zinc chloride.
Further, it is formulated that described catalyst adopts the raw material of following weight portion: 0.8 ~ 1.2 part of stannic chloride, 1.5 ~ 2.5 parts in copper sulphate, 0.8 ~ 1.2 part in sodium chloride, 0.8 ~ 1.2 part in iron chloride, 0.8 ~ 1.2 part in aluminum sulfate, 1.5 ~ 2.5 parts of 0.8 ~ 1.2 part of boric acid and zinc chloride.
Wood modifier of the present invention also comprises water, and its consumption is 50 ~ 200 parts, preferred 70 ~ 180 parts (total amount that all is equivalent to the Wood modifier all the components).
Wherein, described water is running water or demineralized water etc., preferred demineralized water.
The preparation method of described Wood modifier provided by the invention comprises: make phosphoric acid and urea carry out polymerisation under the effect of catalyst.
Particularly, described preparation method comprises: add urea in the phosphoric acid of heating, mix rear continuation heating, add again catalyst, continue again heating, and when the volume of reactant (phosphoric acid and urea after adding catalyst) increases to the twice of original volume, stopped heating; Make afterwards reactant (phosphoric acid and urea behind the adding catalyst) cooling, add BTCA, stir, continue cooling, and get final product; Phosphoric acid, urea, catalyst and BTCA all add in described ratio.
Add entry in described ratio when wherein, adding BTCA.
Wherein, the temperature of phosphoric acid heating is 50 ~ 60 ℃.
Wherein, behind mixed phosphate and the urea, the temperature that continues heating is 90 ~ 120 ℃.
Wherein, behind the adding catalyst, the temperature that continues heating is 130 ~ 140 ℃.
Wherein, it is 60 ~ 80 ℃ to the temperature of reactant (phosphoric acid and urea behind the adding catalyst) cooling.
Wherein, behind the adding BTCA, the temperature that continues cooling is 30 ~ 40 ℃.
Particularly, may further comprise the steps:
1) in reactor, adds phosphoric acid, stir simultaneously heating, make temperature rise to 50 ~ 60 ℃;
2) add urea, the mixture of phosphoric acid and urea is stirred, make feed distribution, be heated evenly, continue heating;
When 3) temperature rises to 110 ~ 120 ℃, in reactor, add catalyst, continue heating;
4) make temperature rise to 130 ~ 140 ℃, and when the volume of reactor internal reaction thing (phosphoric acid and urea after adding catalyst) increases to the twice of original volume, stopped heating;
5) make reactant (phosphoric acid and urea behind the adding catalyst) be cooled to 60 ~ 80 ℃, in reactor, add BTCA and water, stir 25 ~ 35min;
6) continue to be cooled to 30 ~ 40 ℃, discharging is stored.
Modifier of the present invention is the inorganic fire-retarded stabilizing agent of a kind of aqua type nitrogen phosphorus, its advantage applies in the following areas:
1) modifier of the present invention uses BTCA, hydroxyl generation cross-linking reaction in energy and the timber, dimensional stability and the leach resistance of raising timber.
2) not only flame retardant effect is remarkable for modifier of the present invention, and has preferably dimensionally stable function; Process the timber rate of body weight gain about 20%, oxygen index (OI) can reach more than 45%, and dimensional stability ASE can reach more than 20%, and turnover rate is lower than 25%.
3) modifier of the present invention has formaldehyde elimination function equally; Be used for the wood-based plate such as glued board and process, can Effective Raise wood-based plate environmental protection characteristic, burst size of methanal can be stabilized in E
0Level (≤0.5mg/L), have obvious formaldehyde eradicating efficacy.
4) preparation method of modifier of the present invention is simple, and cost is lower; The modifier manufacturing cost of solids content more than 45% is about 3000 yuan/tons, far below the price (about 4000 ~ 6000 yuan/tons) of existing domestic and international fire retardant.
Therefore, Wood modifier provided by the invention is applied in BTCA for the first time the treating of wood field, and cooperates other components, carries out rational proportion, has reached good synergy.Be compared with existing technology, leach resistance is splendid, and the dimensionally stable agent of timber is had larger contribution; And flame retardant effect is excellent equally, and the preparation method is simple, and cost is low.
The specific embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Used herein to material be the conventional material that can buy from the market, can use the product of other specifications, but the specification that limits take the present invention is as excellent.The NM reaction condition of the embodiment of the invention is the routine of this area and selects.
The used demineralized water hardness of the present invention all is lower than 8 degree.
The concentration of phosphoric acid of the present invention is 85%; Nitrogen content is 46.4% in the urea; The purity of BTCA is 99%.Also can use: phosphoric acid concentration is more than 75%, and urea content is more than 46.2%, and the purity of BTCA is more than 95%.The percentage here is mass ratio.
Embodiment 1
One, carry out material preparation by following weight proportion:
Catalyst is the pistac pulvis that prepare voluntarily Beijing Forestry University's material science and technical college environmental protection flame retardant technique center: stannic chloride 40g, copper sulphate 80g, sodium chloride 35g, iron chloride 40g, aluminum sulfate 40g, it is even that boric acid 45g and zinc chloride 70g(proportionally grind rear pulverizing).
Two, preparation method:
1) in the reactor of being furnished with mixer, temperature and pressure display and condenser pipe, add the phosphoric acid in the reaction raw materials, stir simultaneously heating, make temperature rise to 60 ℃;
2) in reactor, add whole urea, simultaneously the mixture of phosphoric acid and urea is proceeded to stir, make material distribute, be heated evenly;
3) continue to heat when making temperature rise to 120 ℃, slowly evenly add catalyst in reactor, mixture is reacted, reaction mass becomes light green color;
4) after the continuation heating makes temperature reach 135 ℃, observing response phenomenon in the time of heating, along with temperature raises, light green color liquid becomes the milky dope gradually, foam sharply increases, rate of rise in temperature is obviously accelerated, the volume of material expands rapidly, and condenser pipe has a large amount of gases to discharge, the stopped heating when volume of question response still internal reaction thing increases to the twice of original volume, continue to stir, material in reactor relies on the heat release of self at vigorous reaction, and temperature continues to rise, and question response tends to be steady, when temperature begins to descend, show that reaction is complete;
5) be cooled to 70 ℃, add BTCA and temperature in the reactor and be 50 ℃ demineralized water, stir 30min;
6) be cooled to 30 ℃, it is for subsequent use to pour products therefrom into containers store.
Three, the technical indicator of product:
Embodiment 2
One, carry out material preparation by following weight proportion:
Catalyst wherein is: stannic chloride 40g, and copper sulphate 135g, sodium chloride 45g, iron chloride 45g, aluminum sulfate 65g, it is even that boric acid 65g and zinc chloride 85g(proportionally grind rear pulverizing).
Two, preparation method:
1) in the reactor of being furnished with mixer, temperature and pressure display and condenser pipe, add the phosphoric acid in the reaction raw materials, stir simultaneously heating, make temperature rise to 50 ℃;
2) in reactor, add urea, simultaneously the mixture of phosphoric acid and urea is proceeded to stir, make material distribute, be heated evenly;
3) continue to heat when making temperature rise to 115 ℃, in reactor, slowly evenly add catalyst, mixture is reacted;
4) after the continuation heating makes temperature reach 140 ℃, observing response phenomenon in the time of heating, along with temperature raises, light green color liquid becomes the milky dope gradually, foam sharply increases, rate of rise in temperature is obviously accelerated, the volume of material expands rapidly, and condenser pipe has a large amount of gases to discharge, the stopped heating when volume of question response still internal reaction thing increases to the twice of original volume, continue to stir, material in reactor relies on the heat release of self at vigorous reaction, and temperature continues to rise, and question response tends to be steady then that temperature no longer rises, when temperature begins to descend, show that reaction is complete;
5) be cooled to 80 ℃, add BTCA and temperature in the reactor and be 50 ℃ demineralized water, stir 35min;
6) be cooled to 30 ℃, it is for subsequent use to pour products therefrom into containers store.
Three, the technical indicator of product:
Embodiment 3
One, carry out material preparation by following weight proportion:
Catalyst wherein is: stannic chloride 35g, and copper sulphate 45g, sodium chloride 35g, iron chloride 35g, aluminum sulfate 25g, it is even that boric acid 25g and zinc chloride 80g(proportionally grind rear pulverizing).
1) in the reactor of being furnished with mixer, temperature and pressure display and condenser pipe, add the phosphoric acid in the reaction raw materials, stir simultaneously heating, make temperature rise to 60 ℃;
2) in reactor, add urea, the mixture of phosphoric acid and urea is proceeded to stir, make material distribute, be heated evenly;
3) continue to heat when making temperature rise to 110 ℃, slowly evenly add catalyst in reactor, mixture is reacted, reaction mass becomes light green color;
4) after the continuation heating makes temperature reach 130 ℃, observing response phenomenon when continuing heating, along with temperature raises, light green color liquid becomes the milky dope gradually, foam sharply increases, and rate of rise in temperature is obviously accelerated, and the volume of material expands rapidly, condenser pipe has a large amount of gases to discharge, be mainly ammonia and steam, water absorbs, the stopped heating when volume of question response still internal reaction thing increases to the twice of original volume, continue to stir, material in reactor relies on the heat release of self at vigorous reaction, and temperature continues to rise, and question response tends to be steady then that temperature no longer rises, when temperature begins to descend, show that reaction is complete;
5) be cooled to 60 ℃, add BTCA and temperature in the reactor and be 50 ℃ demineralized water, stir 25min;
6) be cooled to 40 ℃, it is for subsequent use to pour products therefrom into containers store.
Three, the technical indicator of product:
Embodiment 4
One, carry out material preparation by following weight proportion:
Catalyst ratio wherein is with embodiment 1.
Two, preparation method:
1) in the reactor of being furnished with mixer, temperature and pressure display and condenser pipe, add the phosphoric acid in the reaction raw materials, stir simultaneously heating, make temperature rise to 60 ℃;
2) in reactor, add urea, the mixture of phosphoric acid and urea is proceeded to stir, make material distribute, be heated evenly;
3) continue to heat when making temperature rise to 110 ℃, slowly evenly add catalyst in reactor, mixture is reacted, reactant becomes light green color;
4) after the continuation heating makes temperature reach 130 ℃, observing response phenomenon in the time of heating, along with temperature raises, light green color liquid becomes the milky dope gradually, foam sharply increases, and rate of rise in temperature is obviously accelerated, and the volume of material expands rapidly, condenser pipe has a large amount of gases to discharge, be mainly ammonia and steam, water absorbs, the stopped heating when volume of question response still internal reaction thing increases to the twice of original volume, continue to stir, material in reactor relies on the heat release of self at vigorous reaction, and temperature continues to rise, and question response tends to be steady then that temperature no longer rises, when temperature begins to descend, show that reaction is complete;
5) be cooled to 70 ℃, add BTCA and temperature in the reactor and be 50 ℃ demineralized water, stir 30min;
6) be cooled to 35 ℃, it is for subsequent use to pour products therefrom into containers store.
Three, the technical indicator of product:
Experimental example 1
Adopt respectively the product treatment glued board of the embodiment of the invention 1 ~ 4.
1, experiment material
Veneer: board using poplar board, thickness 1.4 ~ 1.5mm, moisture content 7% ~ 9%, breadth 450 * 450mm;
Adhesive: the homemade modified urea-formaldehyde resin of technology (urea and formaldehyde mole ratio 1:1) routinely, the performance indications of adhesive are as follows:
2, concrete experimental procedure
1) Wood modifier of the embodiment of the invention 1 ~ 4 being made into concentration is 10% the aqueous solution, and veneer is carried out impregnation process 30min;
2) using moisture eliminating drying box, is under 80 ℃ the veneer of processing to be carried out drying to process at baking temperature, and its final moisture content is reached 6 ~ 8%;
3) impregnation: in adhesive, add 15% flour, 1% ammonium chloride, stir;
4) veneer is carried out gluing, glue-spread is the two-sided 280g/m that is coated with
2
5) to colded pressing successively by the sheet material of five layers of veneer assembly, hot pressing, cooling and cutting edge.The pressure of wherein colding pressing is 1 ~ 1.2MPa, and the time of colding pressing is 30min; Hot pressing pressure is 1.2MPa, and hot pressing temperature is 120 ℃, and hot pressing time is 60s/mm.
3, plywood character detects
By GB/T17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " plywood product for preparing is carried out Performance Detection, testing result sees Table 1.
Measure the oxygen index (OI) index of the plywood product of preparation with reference to GB/T2406-93 " Plastics Combustion test method oxygen index method ", testing result sees Table 1.
4, correction data
Contrast groups 1: prepare equally glued board in contrast, except flooding without modifier of the present invention, other preparation processes are identical with this experimental example, and testing result sees Table 1.
Contrast groups 2: adopting commercial a kind of nitrogen-phosphorus is aqua type fire retardant (ammonium polyphosphate flame retardant, the degree of polymerization is less than 20) in contrast, except with this fire retardant 10% concentration of aqueous solution veneer being carried out (without modifier dipping of the present invention) the impregnation process (dipping 30min), other preparation processes are identical with this experimental example, and testing result sees Table 1.
Table 1: plywood character (dipping 30min)
Experimental result in the table 1 shows that modifier of the present invention not only flame retardant effect is remarkable, and has very significantly formaldehyde eradicating efficacy.With the glued board of modifier impregnation process of the present invention, its flame-retardant plywood oxygen index (OI) is more than 45%, and burst size of methanal can be stabilized in E
0Level (≤0.5mg/L).
Experimental example 2
The modifier of the embodiment of the invention 1 ~ 4 is mixed with 10% concentration of aqueous solution, respectively the glued board test specimen that makes in the experimental example is carried out impregnation process 10min, 60 ℃ of dried single board to moisture content be 10 ~ 12%(other with experimental example 1), test various performances by the correlation method in the experimental example 1.
Control group 1: with the contrast groups 1 in the experimental example 1.
Table 2: plywood character (dipping 10min)
Show that from the experimental result of table 2 reduce the dip time of modifier of the present invention, burst size of methanal and oxygen index (OI) all have reduction, mainly are the load capacity that has reduced fire retardant; But all demonstrate good smoke suppressing.
Experimental example 3
Adopt respectively the product treatment cotton wood of embodiment of the invention 1-4.
1, experiment material
Poplar: the age of tree 10 years, sapwood, size (radially * tangential * axially) 30 * 30 * 5mm.
2, by following PROCESS FOR TREATMENT poplar test specimen:
1) modifier with the embodiment of the invention 1 ~ 4 is made into respectively 10% concentration of aqueous solution;
2) the poplar test specimen is used benzene alcohol mixed liquor (2:1) extracting 12 hours before use, puts into 105 ℃ of air dry ovens 12 hours, and the weight of weighing over dry test specimen is also measured its size;
3) test specimen is put in the beaker that fills above-mentioned modifier, pushes down test specimen with stone.Beaker is put into vacuum tank, under vacuum 0.02MPa normal temperature state, kept 0.5 hour; Return to normal pressure, kept 24 hours.Take out test specimen, the surface is wiped away only; Put into 105 ℃ of air dry ovens 12 hours, and measured its weight and size.The test specimen of processing is put into the beaker that fills clear water, guarantee that the water surface covers test specimen.Beaker is put into the dried case of vacuum, and vacuum 0.02MPa kept 0.5 hour, and normal pressure kept 24 hours, measured its weight and size.Test specimen was put into 105 ℃ of air dry ovens 12 hours again, the weight of weighing over dry test specimen is also measured its size.
3, correction data
Control group 2: adopt commercial above-mentioned fire retardant (with experimental example 1), be made into 10% aqueous solution, as stated above poplar is processed.
Table 3: process the test specimen performance
Show that from the experimental result of table 3 with modifier treatment timber of the present invention, the dimensionally stable effect is better, and has good resistance leachability, turnover rate is compared than existing fire retardant, and is very low.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. Wood modifier comprises the raw material of following weight portion: 50 ~ 180 parts of phosphoric acid, 30 ~ 60 parts in urea, 1 ~ 6 part of 0.2 ~ 0.5 part of catalyst and BTCA.
2. Wood modifier according to claim 1 is characterized in that, comprises the raw material of following weight portion: 50 ~ 150 parts of phosphoric acid, 32 ~ 54 parts in urea, 2 ~ 6 parts of 0.25 ~ 0.48 part of catalyst and BTCAs.
3. Wood modifier according to claim 1 and 2 is characterized in that, described catalyst is: stannic chloride, copper sulphate, sodium chloride, iron chloride, aluminum sulfate, boric acid and zinc chloride.
4. Wood modifier according to claim 3, it is characterized in that, described catalyst adopts the raw material of following weight portion formulated: 0.8 ~ 1.2 part of stannic chloride, 1.5 ~ 2.5 parts in copper sulphate, 0.8 ~ 1.2 part in sodium chloride, 0.8 ~ 1.2 part in iron chloride, 0.8 ~ 1.2 part in aluminum sulfate, 1.5 ~ 2.5 parts of 0.8 ~ 1.2 part of boric acid and zinc chloride.
5. the described Wood modifier of any one is characterized in that according to claim 1 ~ 4, and this Wood modifier also comprises water.
6. Wood modifier according to claim 5 is characterized in that, the consumption of described water is 50 ~ 200 parts, preferred 70 ~ 180 parts.
7. the preparation method of the described Wood modifier of claim 1 ~ 6 any one comprises: add urea in the phosphoric acid of heating, mix rear continuation heating, add catalyst, continue again heating, and when the volume of reactant increases to the twice of original volume, stopped heating; Make afterwards the reactant cooling, add BTCA, stir, continue cooling, and get final product; Phosphoric acid, urea, catalyst and BTCA all add in described ratio.
8. preparation method according to claim 7 is characterized in that, adds in proportion entry when adding BTCA.
9. according to claim 7 or 8 described preparation methods, it is characterized in that the temperature of phosphoric acid heating is 50 ~ 60 ℃; Behind mixed phosphate and the urea, the temperature that continues heating is 90 ~ 120 ℃; After adding catalyst, the temperature that continues heating is 130 ~ 140 ℃; Temperature to the reactant cooling is 60 ~ 80 ℃; After adding BTCA, the temperature that continues cooling is 30 ~ 40 ℃.
10. the described preparation method of any one is characterized in that according to claim 7 ~ 9, may further comprise the steps:
1) in reactor, adds phosphoric acid, stir simultaneously heating, make temperature rise to 50 ~ 60 ℃;
2) add urea, the mixture of phosphoric acid and urea is stirred, make feed distribution, be heated evenly, continue heating;
When 3) temperature rises to 110 ~ 120 ℃, in reactor, add catalyst, continue heating;
4) make temperature rise to 130 ~ 140 ℃, and when the volume of reactor internal reaction thing increases to the twice of original volume, stopped heating;
5) make reactant be cooled to 60 ~ 80 ℃, in reactor, add BTCA and water, stir 25 ~ 35min;
6) continue to be cooled to 30 ~ 40 ℃, discharging is stored.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103659970A (en) * | 2013-12-12 | 2014-03-26 | 北京林业大学 | Timber flame retardant modifier and preparation method thereof |
| CN106142260A (en) * | 2016-08-09 | 2016-11-23 | 南京博俊新材料有限公司 | Timber flame retardant modifier based on environmental protection treatment |
| CN106476099A (en) * | 2016-08-26 | 2017-03-08 | 南京博俊新材料有限公司 | A kind of corrosion-resistant Wood modifier and its production method |
| CN106625945A (en) * | 2016-08-26 | 2017-05-10 | 南京博俊新材料有限公司 | Halogen-free flame retardant wood modification agent and production method thereof |
| CN106625946A (en) * | 2016-08-26 | 2017-05-10 | 南京博俊新材料有限公司 | Wood modifying agent and production method thereof |
| CN109968481A (en) * | 2019-05-15 | 2019-07-05 | 赛为木业（石首）有限公司 | A kind of fire retarding wood modifying agent and preparation method thereof |
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| CN102105544A (en) * | 2007-07-02 | 2011-06-22 | 格林百奥生态材料科技（上海）有限公司 | Polymeric composition for cellulosic materials binding and modification |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103659970A (en) * | 2013-12-12 | 2014-03-26 | 北京林业大学 | Timber flame retardant modifier and preparation method thereof |
| CN103659970B (en) * | 2013-12-12 | 2016-08-17 | 北京林业大学 | A kind of timber flame retardant modifier and preparation method thereof |
| CN106142260A (en) * | 2016-08-09 | 2016-11-23 | 南京博俊新材料有限公司 | Timber flame retardant modifier based on environmental protection treatment |
| CN106476099A (en) * | 2016-08-26 | 2017-03-08 | 南京博俊新材料有限公司 | A kind of corrosion-resistant Wood modifier and its production method |
| CN106625945A (en) * | 2016-08-26 | 2017-05-10 | 南京博俊新材料有限公司 | Halogen-free flame retardant wood modification agent and production method thereof |
| CN106625946A (en) * | 2016-08-26 | 2017-05-10 | 南京博俊新材料有限公司 | Wood modifying agent and production method thereof |
| CN109968481A (en) * | 2019-05-15 | 2019-07-05 | 赛为木业（石首）有限公司 | A kind of fire retarding wood modifying agent and preparation method thereof |
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| CN102975250B (en) | 2015-06-03 |
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