CN104987477B - A kind of Nanometer Copper modified low molecular weight phenolic resin and preparation method thereof - Google Patents
A kind of Nanometer Copper modified low molecular weight phenolic resin and preparation method thereof Download PDFInfo
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- CN104987477B CN104987477B CN201510344965.7A CN201510344965A CN104987477B CN 104987477 B CN104987477 B CN 104987477B CN 201510344965 A CN201510344965 A CN 201510344965A CN 104987477 B CN104987477 B CN 104987477B
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- 239000010949 copper Substances 0.000 title claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 36
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000012545 processing Methods 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 164
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 144
- 239000000243 solution Substances 0.000 claims description 108
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 60
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 16
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 15
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 13
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 13
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 13
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 13
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 13
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000002023 wood Substances 0.000 claims description 9
- -1 copper sulphate Disodium ethylene Chemical group 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 229960003339 sodium phosphate Drugs 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007598 dipping method Methods 0.000 abstract description 7
- 239000000523 sample Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- 244000050510 Cunninghamia lanceolata Species 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- VZOPRCCTKLAGPN-UHFFFAOYSA-L potassium;sodium;2,3-dihydroxybutanedioate;tetrahydrate Chemical class O.O.O.O.[Na+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O VZOPRCCTKLAGPN-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
A kind of Nanometer Copper modified low molecular weight phenolic resin and preparation method thereof, this method fabricated in situ Nanometer Copper while Water Solvable Low-molecular Weight Phenol-formaldehyde is prepared, it includes prepolymerization, fabricated in situ Nanometer Copper and polymerize three reactions steps again.The Nanometer Copper modified low molecular weight phenol resin solution of low cost is obtained by simple technique.Timber is carried out after simple vacuum high-pressure dipping using the solution, mechanical property, dimensional stability, the durability of timber are obtained than larger raising, compared with Water Solvable Low-molecular Weight Phenol-formaldehyde (being free of Nanometer Copper) processing, the rotproofness and impact flexibility of timber are also significantly improved.
Description
Technical field：
The present invention relates to a kind of Wooden modifying phenolic resin, and in particular to a kind of Nanometer Copper modified low molecular weight phenolic aldehyde tree
Fat.
Background technology
Resin impregnating processing is the important means of Wooden modifying, and the hardness, compression strength, size that can improve timber are steady
Qualitative and antibiont deterioration, realizes the immortalized utilization of timber.Pf resin of low molecular weight has smaller molecular diameter, energy
It is enough preferably to permeate and be diffused into the spaces at different levels of timber, the modified effect of timber is greatly improved, expands the use of timber
Scope, extend wood-based product service life (money person of outstanding talent wait 2001, the Stamm and Seborg 1936, Rowell such as 2001, Li Jian and
2004, the Wan such as 1991, the Furuno such as Banks 1985, Ryu and Kim 2008).
Water Solvable Low-molecular Weight Phenol-formaldehyde using the water of small molecule as solvent, can not only preferably swollen timber, carry
High modified effect, and safety and environmental protection, meet expanding economy trend.But, after Water Solvable Low-molecular Weight Phenol-formaldehyde dipping
Timber, toughness declines, and antiseptic power is limited, if being processed into outdoor product (such as often by sitting the outdoor chair for pressing impact
Stool, console table, floor etc.), destruction usually occurred after 2 to 5 years and rotten, service life is limited.Some researchers are by water solubility
Timber after pf resin of low molecular weight dipping, is placed under the hot press of high temperature, and wood surface is compressed and solidified, surface is made close
Realification timber, although so improving the dimensional stability of timber, mechanical property and durability, complex process, equipment is held high
It is expensive that (2004) money person of outstanding talent waits 2001, Liu Junliang etc..
Nanometer Copper has many excellent performances, polymer-modified makes the mechanical property particularly toughness of polymer with it
It is significantly improved, if it is distributed in timber, can also effectively improves the preservation of timber against decay performance.However, nanometer copper processing is high
It is expensive, 100 grams of Nanometer Copper prices up to 700 yuan, moreover, when being added directly as modifying agent, influenceed by nano effect, nanometer copper-base
Easily reunite in treatment fluid, so as to significantly reduce treatment effect (Lin Rong can wait 2004).
The content of the invention
It is an object of the invention to provide a kind of Nanometer Copper modified low molecular weight phenolic resin and preparation method thereof, this method exists
Fabricated in situ Nanometer Copper while preparing Water Solvable Low-molecular Weight Phenol-formaldehyde, the nanometer of low cost is obtained by simple technique
Copper modified low molecular weight phenol resin solution.Timber is carried out after simple vacuum high-pressure dipping using the solution, the power of timber
Learn property, dimensional stability, durability to obtain than larger raising, (be free of and receive with Water Solvable Low-molecular Weight Phenol-formaldehyde
Rice copper) handle and compare, the rotproofness and impact flexibility of timber are also significantly improved.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of Nanometer Copper modified low molecular weight phenolic resin, comprises the following steps：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1~2 parts by weight is dissolved in 4~6 parts by weight distilled water, to the copper sulphate
Disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and polyethylene are added in the aqueous solution
The mass ratio of pyrrolidones is 1: (0.5~1.6): (0.01~0.1), adjust pH to 7-12 with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 1~3 parts by weight is dissolved in 0.1~1.0 parts by weight distilled water, to the formalin
The mass ratio of addition sodium pyrophosphate and sodium potassium tartrate tetrahydrate in solution, sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate is (0.1
~0.8): (0.1~1.2): 1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 3~7 parts by weight concentration are 30-50wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 6~10 parts by weight are mixed, add 0.1 into mixture at 40~60 DEG C~
The sodium hydroxide solution that 0.5 parts by weight step I is prepared；Temperature is then risen to 70-90 DEG C, it is small in 0.8~1.5 at such a temperature
When the sodium hydroxide solution prepared of interior addition 0.5~1.1 parts by weight step I；The formaldehyde of 1.5~2.0 parts by weight is subsequently added, plus
Solution is set to keep 70-90 DEG C of 1-2h after complete；
III. fabricated in situ Nanometer Copper
By the step II prepolymer solutions prepared be rapidly cooled to less than 60 DEG C and add step I preparation formaldehyde mix it is molten
Liquid, is stirred, and pH to 10-13 is adjusted with sodium hydroxide solution in 20min；Then added under 40-60 DEG C, high-speed stirred
The copper-bath that step I is prepared, pH to 10-13 is adjusted in 20min with sodium hydroxide solution, and continuation is reacted at such a temperature
0.3~0.5h, obtains Nanometer Copper and is modified prepolymer solution；
IV. it polymerize again
Nanometer Copper prepared by step III is modified prepolymer solution under high velocity agitation in 0.1~0.5h by reaction solution
Temperature rises to 60-100 DEG C, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.3~0.6h at this temperature.
Preparation method as described above, it is preferable that this method comprises the following steps：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1~1.5 parts by weight is dissolved in 5~6 parts by weight distilled water, to the sulfuric acid
Disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and poly- second are added in copper liquor
The mass ratio of alkene pyrrolidone is 1: (0.8~1.6): (0.01~0.07), adjust pH to 7-12 with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 1~2 parts by weight is dissolved in 0.4~1.0 parts by weight distilled water, to the formalin
The mass ratio of addition sodium pyrophosphate and sodium potassium tartrate tetrahydrate in solution, sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate is (0.1
~0.5): (0.2~0.6): 1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 5~7 parts by weight concentration are 30-50wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 6~9 parts by weight are mixed, add 0.1 into mixture at 40~60 DEG C~
The sodium hydroxide solution that 0.4 parts by weight step I is prepared；Temperature is then risen to 70~90 DEG C, at such a temperature in 1 hour plus
Enter the sodium hydroxide solution of 0.5~0.9 parts by weight step I preparations；The formaldehyde of 1.6~2.0 parts by weight is subsequently added, is made after adding
Solution keeps 70-90 DEG C of 1-2h, obtains prepolymer solution；
III. the step II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C by fabricated in situ Nanometer Copper, and add step
The formaldehyde mixed solution that rapid I is prepared, is stirred, and pH to 11~13 is adjusted with sodium hydroxide solution in 20min；Then 40
~60 DEG C, add the copper-bath that step I is prepared under high-speed stirred, adjust pH to 11 with sodium hydroxide solution in 20min
~13, continue to react 0.3~0.5h at such a temperature, obtain Nanometer Copper and be modified prepolymer solution；
IV. it polymerize again
Nanometer Copper prepared by step III is modified prepolymer solution under high velocity agitation in 0.1~0.5h by reaction solution
Temperature rises to 70~100 DEG C, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.3~0.6h at this temperature.
Preparation method as described above, it is preferable that the gross weight that sodium hydroxide is added in the step II is phenol weight
0.11~0.35 times.
Preparation method as described above, it is preferable that the rotating speed of the high-speed stirred is 2000~6000 turns/min.
Preparation method as described above, it is preferable that methods described comprises the following steps：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1 parts by weight is dissolved in 5 parts by weight distilled water, to the copper sulfate solution
Middle addition disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and polyvinylpyrrolidine
The mass ratio of ketone is 1: 1.6: 0.05, and pH to 7-12 is adjusted with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 2 parts by weight is dissolved in 0.7 parts by weight distilled water, added into the formalin
Enter sodium pyrophosphate and sodium potassium tartrate tetrahydrate, the mass ratio of sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate is 0.35: 0.55: 1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 6 parts by weight concentration are 40wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 7 parts by weight are mixed, 0.4 parts by weight step I is added into mixture at 40 DEG C
The sodium hydroxide solution of preparation；Temperature is then risen to 85 DEG C, matched somebody with somebody at such a temperature in adding 0.8 parts by weight step I in 1 hour
The sodium hydroxide solution of system；The formaldehyde of 1.8 parts by weight is subsequently added, solution is kept 90 DEG C of 2h after adding, performed polymer is obtained molten
Liquid；
III. fabricated in situ Nanometer Copper
The step II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C, and add the formaldehyde mixing of step I preparations
Solution, is stirred, and pH to 11 is adjusted with sodium hydroxide solution in 20min；Then add under 60 DEG C, 3000 turns/min stirrings
Enter the copper-bath of step I preparations, pH to 11.5 is adjusted with sodium hydroxide solution in 20min, continue anti-at such a temperature
0.5h is answered, Nanometer Copper is obtained and is modified prepolymer solution；
IV. it polymerize again
Nanometer Copper modification prepolymer solution prepared by step III is under 3000 turns/min stirrings by reaction solution in 0.2h
Temperature rises to 90 DEG C, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.6h at this temperature.
On the other hand, the present invention provides a kind of Nanometer Copper modified low molecular weight phenolic resin, and it is using as described above
Prepared by method.
Another aspect, the present invention provides Nanometer Copper modified low molecular weight phenolic resin as described above in processing timber
Using.
Another further aspect, the present invention provides a kind of phenolic resin modified timber, and the timber is changed using Nanometer Copper as described above
Property pf resin of low molecular weight impregnation process.
Phenolic resin modified timber as described above, it is preferable that the impregnation process method includes：Timber is placed in processing
In tank, -0.03~-0.10MPa is evacuated to, 10~40min of the vacuum is kept, then with institute of the concentration for 15~35g/L
Nanometer Copper modified low molecular weight phenolic resin aqueous solution impregnation process is stated, and is progressively pressurized to 0.3~0.8MPa, the pressure process
Continue 4~7h, the sample impregnated is continued to be immersed in 8~24h in process tank after release.
The present invention is the synthesizing water-solubility pf resin of low molecular weight while, and fabricated in situ Nanometer Copper makes Nanometer Copper equal
It is dispersed in evenly in Water Solvable Low-molecular Weight Phenol-formaldehyde solution, the solution has certain viscosity, it is suppressed that the reunion of Nanometer Copper,
The preparation cost of Nanometer Copper is greatly reduced, preparation technology is simplified.The preparation method is divided into three steps：
(1) prepolymerization：The key of the step is the control degree of polymerization, the phenolic resin of small-molecular-weight is generated, by two batches
Catalyst sodium hydroxide is added, and controlling reaction temperature is at 70-90 DEG C, makes generation phenolic resin molecular weight 320~592.
(2) fabricated in situ Nanometer Copper：The key of the step is to prevent from making Nanometer Copper is dispersed to prevent from reuniting.On the one hand,
Disodium ethylene diamine tetraacetate and polyvinylpyrrolidone can improve dispersiveness as metal-chelator with copper ion complexing；It is another
Aspect, as added in the formalin of solvent dispersant sodium pyrophosphate and complexing agent sodium potassium tartrate tetrahydrate contribute to emulsifying soln and
Stable system.
(3) it polymerize again：Continue reaction a period of time after synthetizing nano-copper at 60-100 DEG C, make Nanometer Copper and phenolic resin body
System is sufficiently mixed, and makes the formaldehyde of free state, phenol continue to polymerize.
Vacuum high-pressure impregnation process is carried out to Cunninghamia lanceolata using the mixed solution, the surface for not only eliminating the later stage is close
Realification step, simplifies production technology, has saved the energy, and every mechanical property of processing material can be made, it is dimensional stability, resistance to
Long property is obtained for larger raising, compared with Water Solvable Low-molecular Weight Phenol-formaldehyde (being free of Nanometer Copper) processing, timber it is resistance to
Corruption and impact flexibility are also significantly improved, and the material is particularly suitable for use in the former material of outdoor furniture and other woodworks
Material.
Embodiment
The preparation method of the present invention is further elaborated on below by embodiment.
Embodiment 1 prepares Nanometer Copper modified low molecular weight phenolic resin (one)
I. following three kinds of solution are configured：
Copper sulphate mixed solution：37.45g copper sulphate is dissolved in 220g distilled water, added into the copper sulfate solution
Enter 58g disodium ethylene diamine tetraacetates and 1.5g polyvinylpyrrolidones, pH to 11 is adjusted with sodium hydrate aqueous solution；
Formaldehyde mixed solution：75g formaldehyde is dissolved in 40g distilled water, 8g pyrophosphoric acids are added into the formalin
Sodium and 20g sodium potassium tartrate tetrahydrates；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 200g concentration is 40wt%.
II. phenol (150g) and formaldehyde (200g) are added into three-necked flask, heating water bath makes mixture temperature be 40 DEG C
Afterwards, the sodium hydroxide solution (15g) that concentration is 40wt% is added.Temperature is then risen to 85 DEG C, added in one hour
40wt% sodium hydroxide solutions (20g), and maintain the temperature at 85 DEG C or so, cooled down when temperature is more than 90 DEG C with cold water.Hydrogen-oxygen
After change sodium solution is added, formaldehyde (68g) is added, solution is kept 90 DEG C of 2h after adding.
III. it is rapidly cooled to less than 60 DEG C by the step II prepolymer solutions prepared and adds the formaldehyde that step I prepares mix
Solution is closed, the sodium hydroxide solution regulation pH to 12 for stirring and being 40wt% with concentration adjusts pH to be completed in 20min.Connect
40 DEG C, 3000 turns/min stirrings it is lower add copper-bath that step I prepares (copper sulphate reacts generation hydrogen with formaldehyde,
A bottleneck must be opened), and with the pH value of acidometer monitoring reaction solution, add sodium hydroxide solution to control the pH of reaction solution to exist
12, adjust pH to be completed in 20min, 0.5h is reacted in continuation at such a temperature.
IV. the Nanometer Copper prepared by step III is modified prepolymer solution will be anti-in 0.3h under 2000 turns/min stirrings
Answer liquid temperature degree to rise to 90 DEG C, continue to be rapidly cooled to discharge at 40 DEG C after reacting 0.6h at this temperature, obtain Nanometer Copper and be modified
Pf resin of low molecular weight sample (one).
Gained Nanometer Copper modified phenolic resin lipoprotein solution is bronzing transparency liquid, and pH value is 11.57 (to be surveyed during 25 DEG C of temperature
Amount), viscosity is 18.8mpas (BROOK FIELD AT85442), and solid contents is 45%, and polymer is with 3 to 4 polymerizations
Based on degree, being distributed in molecular weight between 456 to 592 more.
Embodiment 2 prepares Nanometer Copper modified low molecular weight phenolic resin (two)
I. following three kinds of solution are configured：
Copper sulphate mixed solution：37.45g copper sulphate is dissolved in 187.25g distilled water, into the copper sulfate solution
59.92g disodium ethylene diamine tetraacetates and 1.87g polyvinylpyrrolidones are added, pH to 11 is adjusted with sodium hydrate aqueous solution；
Formaldehyde mixed solution：74.90g formaldehyde is dissolved in 26.22g distilled water, added into the formalin
13.11g sodium pyrophosphates and 20.60g sodium potassium tartrate tetrahydrates；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 224.70g concentration is 40wt%.
II. phenol (180g) and formaldehyde (262g) are added into three-necked flask, heating water bath makes mixture temperature be 40 DEG C
Afterwards, the sodium hydroxide solution (15g) that concentration is 40wt% is added.Temperature is then risen to 85 DEG C, added in one hour
40wt% sodium hydroxide solution (30g), and maintain the temperature at 85 DEG C or so, cooled down when temperature is more than 90 DEG C with cold water.Hydrogen
After sodium hydroxide solution is added, formaldehyde (67.41g) is added, solution is kept 90 DEG C of 2h after adding.
III. the rapid II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C and add the formaldehyde mixing that step I is prepared
Solution, the sodium hydroxide solution regulation pH to 11 for stirring and being 40wt% with concentration, adjusts pH to be completed in 20min.Then
Copper-bath (copper sulphate and formaldehyde reaction generation hydrogen, palpus that step I is prepared are added under 60 DEG C, 3000 turns/min stirrings
Open a bottleneck), and with the pH value of acidometer monitoring reaction solution, add sodium hydroxide solution to control the pH of reaction solution to exist
11.5, adjust pH to be completed in 20min, 0.5h is reacted in continuation at such a temperature.
IV. the Nanometer Copper prepared by step III is modified prepolymer solution will be anti-in 0.2h under 3000 turns/min stirrings
Answer liquid temperature degree to rise to 90 DEG C, continue to be rapidly cooled to discharge at 40 DEG C after reacting 0.6h at this temperature, obtain Nanometer Copper and be modified
Pf resin of low molecular weight sample (two).
Gained Nanometer Copper modified phenolic resin lipoprotein solution is bronzing transparency liquid, and pH value is 11.07 (to be surveyed during 25 DEG C of temperature
Amount), viscosity is 13.8mPas (BROOK FIELD AT85442), and solid contents is 40%, and polymer is with 2 to 4 polymerizations
Based on degree, i.e. molecular weight is distributed between 320 to 592 more based on 456.
The phenolic resin modified timber of Nanometer Copper modified low molecular weight of embodiment 3
First, Nanometer Copper modified low molecular weight resin impregnating timber
Sample (one) and sample (two) prepared by embodiment 1,2 is configured to the aqueous solution that phenolic resin concentration is 25g/L.
The method that processing is impregnated using vacuum high-pressure, timber is placed in process tank, -0.03MPa is evacuated to, the vacuum is kept
30min, the Nanometer Copper modified low molecular weight phenolic resin aqueous solution impregnation process for being then 25g/L with concentration, and progressively
0.5MPa is pressurized to, the pressure process continues 5h, continues to be immersed in 16h in process tank by the sample impregnated after release.Dipping
Gas is done to moisture content 16% or so afterwards, and then oven for drying is weighed, and obtains the phenolic resin modified wood of Nanometer Copper modified low molecular weight
Material.
2nd, performance test
(1) compression strength
Experimental method：The parallel-to-grain compressive strength of timber is determined according to national standard GB1935-91.
Experimental procedure：Timber chooses the sapwood region of Cunninghamia lanceolata, by sample in order sawing into 20*20*30 (L)
Mm, 5 groups of totally 15 samples, one group of sample is essentially the adjacent position for coming from same section of timber.In all samples, processing
Group Sample A and B are respectively the timber for the resin solution dipping acquisition that above step one is prepared with Examples 1 and 2, control sample
Do not handle.The preposition moisture content that adjusted in climatic chamber of compression test carries out related examination to 12% according to national standard GB1935-91
Test and test.
The China fir parallel-to-grain compressive strength test data of table 1
Test result as shown in table 1, the untreated high 20%-30% of the compressive strength rate of sample after as a result explanation processing.
(2) impact flexibility
Experimental method：The impact flexibility of timber is determined according to national standard GB1940-91.
Experimental procedure：Choose the sapwood region of Cunninghamia lanceolata, by sample in order sawing into 20*20*300 (L) mm, 6
Totally 24 samples are organized, one group of sample is essentially the adjacent position for coming from same section of timber.In all samples, 1,5,9,
13rd, 17, No. 21 samples are that (process for preparing resins is standby just with the resin-made that Nanometer Copper is modified for Water Solvable Low-molecular Weight Phenol-formaldehyde
Method is similar, it is only necessary to save step I and III, 2,6,10,14,18, No. 22 samples be Nanometer Copper modified water-soluble prepared by embodiment 1
Property pf resin of low molecular weight treatment group, 3,7,11,15,19, No. 23 samples be Nanometer Copper modified soluble prepared by embodiment 2
Pf resin of low molecular weight treatment group, remaining 6 sample are not handled as a control group.Impact flexibility test is preposition in constant temperature and humidity
Moisture content is adjusted in case to 12%.Then, correlation test is carried out according to national standard GB 1940-91.
Table 2
Test result as shown in table 2, as a result illustrates after the processing of Nanometer Copper modified soluble pf resin of low molecular weight, sample
Impact flexibility than Water Solvable Low-molecular Weight Phenol-formaldehyde processing improve 10% or so.
(3) the swollen property test of moisture-resistant
Experimental method：The anti-harmomegathus rate of timber is determined according to national standard GB1934.2-91.
Experimental procedure：The sapwood region of Cunninghamia lanceolata is chosen, sawing is into 20*20*20mm in order by sample, and 5 groups are total to
15 samples, one group of sample is essentially the adjacent position for coming from same section of timber.In all samples, treatment group Sample A
It is respectively the timber for the resin solution dipping acquisition that above step one is prepared with Examples 1 and 2 with B, remaining control sample is not located
Reason.The preposition moisture content that adjusted in climatic chamber of property that moisture-resistant is swollen test is to 12%.Then, enter according to national standard GB1934.2-91
Row correlation test and test.
Table 3
| Sample number into spectrum | Moisture-resistant is swollen coefficient | Coefficient increment rate that moisture-resistant is swollen (100%) |
| 1 processing A | 10.83 | 24.42 |
| 2 processing B | 10.64 | 25.76 |
| 3 controls | 14.33 | - |
| 4 processing A | 11.27 | 27.24 |
| 5 processing B | 10.80 | 30.28 |
| 6 controls | 15.49 | - |
| 7 processing A | 6.84 | 21.92 |
| 8 processing B | 6.76 | 22.87 |
| 9 controls | 8.76 | - |
| 10 processing A | 11.25 | 25.40 |
| 11 processing B | 10.04 | 33.39 |
| 12 controls | 15.08 | - |
| 13 processing A | 10.13 | 30.09 |
| 14 processing | 10.29 | 28.96 |
| 15 controls | 14.49 | - |
Test result as shown in table 3, as a result illustrates sample after the processing of Nanometer Copper modified soluble pf resin of low molecular weight
Bulking coefficient ratio untreated reduce 30% or so.
(4) resistance to decadent nature：
Experimental method：The resistance to white rot performance of poplar is determined according to national standard GB/T 13942.1-2009.
Experimental procedure：Choose the poplar of artificial forest 72, by sample in order sawing into 20*20*10 (L) mm, 24, sample.It is all
Sample comes from the close position of same section of timber in principle.In all samples, 1 to No. 6 samples are receiving for the preparation of embodiment 1
Rice copper modified soluble pf resin of low molecular weight treatment group, 6 to No. 12 samples are Nanometer Copper modified water-soluble prepared by embodiment 2
Property pf resin of low molecular weight treatment group, remaining sample is not handled.Treatment group is wrapped with active paper, normal in steam sterilizer
Or so half an hour is kept under the conditions of pressure, makes moisture content to 40%-60%, can be according to national standard GB/T 13942.1- after cooling
2009 are tested and are tested.
Table 4
| Sample number into spectrum | Resistance to white rot |
| No. 1-6 | Corrosion resistant level |
| No. 6-12 | Corrosion resistant level |
| No. 7-24 | Not corrosion resistant level |
Test result as shown in table 4, as a result illustrates that resin solution prepared by embodiment 1,2 can make the sample after processing
Resistance to white rot brings up to two grades from level Four, i.e., never corrosion resistant level is promoted to corrosion resistant level.
Claims (7)
1. a kind of method for improving Wood mechanical property and moisture-resistant decay resistance, it is characterised in that be modified using Nanometer Copper low
Molecular weight phenolic resin impregnation process timber, the preparation method of the Nanometer Copper modified low molecular weight phenolic resin includes following step
Suddenly：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1~2 parts by weight is dissolved in 4~6 parts by weight distilled water, it is water-soluble to the copper sulphate
Disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and polyvinyl pyrrole are added in liquid
The mass ratio of alkanone is 1: (0.5~1.6): (0.01~0.1), adjust pH to 7-12 with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 1~3 parts by weight is dissolved in 0.1~1.0 parts by weight distilled water, to the formalin
Middle addition sodium pyrophosphate and sodium potassium tartrate tetrahydrate, the mass ratio of sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate for (0.1~
0.8): (0.1~1.2): 1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 3~7 parts by weight concentration are 30-50wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 6~10 parts by weight are mixed, 0.1~0.5 weight is added into mixture at 40~60 DEG C
Measure the sodium hydroxide solution that part step I is prepared；Temperature is then risen to 70-85 DEG C, at such a temperature in 0.8~1.5 hour
Add the sodium hydroxide solution that 0.5~1.1 parts by weight step I is prepared；The formaldehyde of 1.5~2.0 parts by weight is subsequently added, after adding
Solution is set to keep 70-90 DEG C of 1-2h；
III. fabricated in situ Nanometer Copper
The step II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C and the formaldehyde mixed solution of step I preparations is added,
Stir, pH to 10-13 is adjusted with sodium hydroxide solution in 20min；Then step is added under 40-60 DEG C, high-speed stirred
The copper-bath that rapid I is prepared, pH to 10-13 is adjusted in 20min with sodium hydroxide solution, and continuation is reacted at such a temperature
0.3~0.5h, obtains Nanometer Copper and is modified prepolymer solution；
IV. it polymerize again
Nanometer Copper prepared by step III is modified prepolymer solution under high velocity agitation in 0.1~0.5h by reacting liquid temperature
60-100 DEG C is risen to, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.3~0.6h at this temperature.
2. the method according to claim 1 for improving Wood mechanical property and moisture-resistant decay resistance, it is characterised in that institute
The preparation method for stating Nanometer Copper modified low molecular weight phenolic resin comprises the following steps：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1~1.5 parts by weight is dissolved in 5~6 parts by weight distilled water, to the sulfuric acid copper water
Disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and polyethylene pyrrole are added in solution
The mass ratio of pyrrolidone is 1: (0.8~1.6): (0.01~0.07), adjust pH to 7-12 with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 1~2 parts by weight is dissolved in 0.4~1.0 parts by weight distilled water, to the formalin
Middle addition sodium pyrophosphate and sodium potassium tartrate tetrahydrate, the mass ratio of sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate for (0.1~
0.5): (0.2~0.6): 1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 5~7 parts by weight concentration are 30-50wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 6~9 parts by weight are mixed, 0.1~0.4 weight is added into mixture at 40~60 DEG C
Measure the sodium hydroxide solution that part step I is prepared；Temperature is then risen to 70~90 DEG C, at such a temperature in adding 0.5 in 1 hour
The sodium hydroxide solution that~0.9 parts by weight step I is prepared；The formaldehyde of 1.6~2.0 parts by weight is subsequently added, makes solution after adding
70-90 DEG C of 1-2h is kept, prepolymer solution is obtained；
III. the step II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C by fabricated in situ Nanometer Copper, and add step I
The formaldehyde mixed solution of preparation, is stirred, and pH to 11~13 is adjusted with sodium hydroxide solution in 20min；Then 40~
60 DEG C, add the copper-bath that step I is prepared under high-speed stirred, in 20min with sodium hydroxide solution adjust pH to 11~
13, continue to react 0.3~0.5h at such a temperature, obtain Nanometer Copper and be modified prepolymer solution；
IV. it polymerize again
Nanometer Copper prepared by step III is modified prepolymer solution under high velocity agitation in 0.1~0.5h by reacting liquid temperature
70~100 DEG C are risen to, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.3~0.6h at this temperature.
3. the method according to claim 2 for improving Wood mechanical property and moisture-resistant decay resistance, it is characterised in that institute
State the gross weight of sodium hydroxide is added in step II for phenol weight 0.11~0.35 times.
4. the method according to claim 2 for improving Wood mechanical property and moisture-resistant decay resistance, it is characterised in that institute
The rotating speed for stating high-speed stirred is 2000~6000 turns/min.
5. the method according to claim 2 for improving Wood mechanical property and moisture-resistant decay resistance, it is characterised in that institute
The preparation method for stating Nanometer Copper modified low molecular weight phenolic resin comprises the following steps：
I. following three kinds of solution are configured：
Copper sulphate mixed solution：The copper sulphate of 1 parts by weight is dissolved in 5 parts by weight distilled water, added into the copper sulfate solution
Enter disodium ethylene diamine tetraacetate and polyvinylpyrrolidone, copper sulphate, disodium ethylene diamine tetraacetate and polyvinylpyrrolidone
Mass ratio is 1: 1.6: 0.05, and pH to 7-12 is adjusted with sodium hydrate aqueous solution；
Formaldehyde mixed solution：The formaldehyde of 2 parts by weight is dissolved in 0.7 parts by weight distilled water, added into the formalin burnt
The mass ratio of sodium phosphate and sodium potassium tartrate tetrahydrate, sodium pyrophosphate, sodium potassium tartrate tetrahydrate and above-mentioned copper sulphate is 0.35：0.55∶1；
Sodium hydroxide solution：Prepare the sodium hydrate aqueous solution that 6 parts by weight concentration are 40wt%；
II. prepolymerization
The phenol of 5 parts by weight and the formaldehyde of 7 parts by weight are mixed, 0.4 parts by weight step I preparations are added into mixture at 40 DEG C
Sodium hydroxide solution；Temperature is then risen to 85 DEG C, at such a temperature in added in 1 hour 0.8 parts by weight step I preparation
Sodium hydroxide solution；The formaldehyde of 1.8 parts by weight is subsequently added, solution is kept 90 DEG C of 2h after adding, prepolymer solution is obtained；
III. fabricated in situ Nanometer Copper
The step II prepolymer solutions prepared are rapidly cooled to less than 60 DEG C, and add the formaldehyde mixed solution of step I preparations,
Stir, pH to 11 is adjusted with sodium hydroxide solution in 20min；Then step is added under 60 DEG C, 3000 turns/min stirrings
The copper-bath that rapid I is prepared, pH to 11.5 is adjusted in 20min with sodium hydroxide solution, and continuation is reacted at such a temperature
0.5h, obtains Nanometer Copper and is modified prepolymer solution；
IV. it polymerize again
Nanometer Copper modification prepolymer solution prepared by step III is under 3000 turns/min stirrings by reacting liquid temperature in 0.2h
90 DEG C are risen to, continues to react that 40 DEG C, discharging are rapidly cooled to after 0.6h at this temperature.
6. the method for improving Wood mechanical property and moisture-resistant decay resistance according to any one of claim 1-5, its
It is characterised by, the use Nanometer Copper modified low molecular weight resin impregnating processing timber method includes：Timber is placed in place
Manage in tank, be evacuated to -0.03~-0.10MPa, keep 10~40min of the vacuum, be then 15~35g/L's with concentration
The Nanometer Copper modified low molecular weight phenolic resin aqueous solution impregnation process, and 0.3~0.8MPa is progressively pressurized to, this pressurizeed
4~7h of Cheng Chixu, continue to be immersed in 8~24h in process tank after release by the sample impregnated.
7. a kind of phenolic resin modified timber, it is characterised in that the timber is using the method any one of claim 1-6
Prepare.
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