CN108705635A - A kind of enhancing modified artificial forest wood preparation method - Google Patents
A kind of enhancing modified artificial forest wood preparation method Download PDFInfo
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- CN108705635A CN108705635A CN201810491117.2A CN201810491117A CN108705635A CN 108705635 A CN108705635 A CN 108705635A CN 201810491117 A CN201810491117 A CN 201810491117A CN 108705635 A CN108705635 A CN 108705635A
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- 239000002023 wood Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 40
- 239000005011 phenolic resin Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 65
- 230000008569 process Effects 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 β-aminoethyl Chemical group 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000003063 flame retardant Substances 0.000 abstract description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 235000019256 formaldehyde Nutrition 0.000 description 16
- 229960004279 formaldehyde Drugs 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 241000219000 Populus Species 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 229920003180 amino resin Polymers 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 244000050510 Cunninghamia lanceolata Species 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195955 Equisetum hyemale Species 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 235000005456 Pinus sylvestris var mongolica Nutrition 0.000 description 1
- 241000114025 Pinus sylvestris var. mongolica Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/005—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising microparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/20—Removing fungi, molds or insects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/30—Fireproofing
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The present invention is a kind of enhancing modified artificial forest wood preparation method, its main feature is that, including in have：The preparation of phenol resin solution, the preparation of modified-silicate solution, the preparation of composite modifier and carry out that dipping is modified to obtain modified artificial forest wood with drying process to timber, specific preparation process is as follows：The preparation of phenol resin solution, the preparation of modified-silicate solution, the preparation of composite modifier and to carry out dipping to timber modified and be dried.Due to the introducing of inorganic material, the physical and mechanical properties such as density of wood, hardness, dimensional stability are being improved, it is especially obvious to the improvement of the shock resistance of timber, while compared with similar technique, the flame retardant property of modified material improves a lot.Treated, and timber can be widely applied to the industries such as building, furniture, floor decorative material.
Description
Technical field
The present invention relates to a kind of enhancing improved woods, and in particular to a kind of enhancing modified artificial forest wood preparation method.
Background technology
Timber there are materials it is soft, density is low, variability is big, poor dimensional stability the problems such as, greatly limit its apply model
It encloses, cannot be directly used to the productions such as solid wood furniture, floor.Enhancing modification is carried out to artificial forest wood to attract wide attention and grind
Study carefully.Amino resins can improve artificial forest wood case hardness and dimensional stability, static bending strength, pressure resistance to Wooden modifying
The mechanical properties such as degree.Density increases after the modified melmac of poplar or Lauxite modification, except impact flexibility has
Outside reducing, other performances all increase.Hot pressing is modified after having carried out Lauxite dipping to fast-growing Chinese fir, the results showed that speed
Raw China fir is modified material static bending strength and averagely improves 42%, and Deflection Modulus of Elasticity averagely improves 17%.Modified cyanurotriamide resin and
Lauxite enhances improved wood, is at resin by detecting aldehyde compound, alkane compound, formaldehyde to total organic volatile
Manage the key component of the volatile organic contaminant of poplar reinforced material release, wherein burst size of methanal formaldehyde mass concentration from
0.14mg·m-3First increase to 0.17mgm-3；It is 2.5m in useful load2·m-3Exceed China's formaldehyde in indoor air down to limit the quantity
It is worth (0.08mgm-3).Product after phenolic resin is cured has good heat-resisting and mechanical property, and performance is stablized.But phenol
Urea formaldehyde has some disadvantages that it is prevented to be applied in Wood composite material, such as high solidification temperature, relatively slow solidification rate, compared with
It is crisp, toxicity and dark colour.Improve these properties, including uses different catalysts, additive or improvement resin formula.Due to phenol
Urea formaldehyde enbrittles, thus increase weight it is larger when their parallel-to-grain compressive strength instead than increase weight it is smaller when it is low.The impact of modified material
Toughness is less than material, and increases toughness with WPG and decline.Since phenolic resin itself enbrittles and modification is solid at high temperature
Change can also become fragile, therefore the impact toughness decreased of modified material.There is also the larger problems of brittleness after solidification for same amino resins.CN
A kind of 101664945 enhancings, flame-retardant modified artificial forest wood and preparation method thereof, timber is handled using amino resins and boron, by
It can not react with amino resins in boron is simply added, and there are Form aldehyde release harm for the amino resins after solidification.Profit
Enhancing modification is carried out to timber with organic monomer, the results showed that while increasing property, dive in this article manufacturing process
There are environmental pollution and product, there are TVOC releases.
Invention content
It is an object of the present invention to provide a kind of enhancing modified artificial forest wood preparation method, this method utilizes silicate/phenolic aldehyde
The soft material of resin Combined Treatment artificial forest, silicate improve the brittleness technology of phenolic resin, reduce the solidification temperature of phenolic resin
Degree and shortening hardening time increase the physical and mechanical property of modified material, especially make shock resistance；At the same time, due to silicic acid
The introducing of salt can play the portion void of the closing soft material of artificial forest, therefore it is soft to reduce artificial forest to a certain extent
The Form aldehyde release of material itself.In addition silicate has the characteristics that at low cost, nontoxic and environmentally friendly, therefore the introducing energy of silicate
Enough reduction phenolic resin costs by a relatively large margin, to reduce the cost of material of modified material.
Realize the object of the invention the technical solution adopted is that, a kind of enhancing modified artificial forest wood preparation method, feature
Be, it include in have：The preparation of phenol resin solution, the preparation of modified-silicate solution, the preparation of composite modifier and
Timber impregnate being modified and obtains modified artificial forest wood with drying process, specific preparation process is as follows：
1) preparation of phenol resin solution
Phenol, formaldehyde, aqueous slkali and water molar ratio be 1:2.0~2.4:0.2~0.6:4.0~4.5；By phenol, alkali
Solution and water are put into reaction kettle successively, are then heated to 40~45 DEG C, are slowly added to the formaldehyde of formaldehyde total amount 80%, are risen
80~85 DEG C of temperature carries out first stage reaction, in 50~60 minutes reaction time, obtains first stage reaction solution；Will be obtained again
One stage reaction solution cools down 40~50 DEG C, and the formaldehyde of formaldehyde total amount residue 20% is added, and adds and is to slowly warm up to 90~92 DEG C, and
Viscosity is measured by sampling at this temperature, when viscosity reaches 40~300mPas, it is molten to be cooled to the obtained phenolic resin of 40 DEG C of blowings
Liquid；
2) preparation of modified-silicate solution
The weight ratio of coupling agent and silicate solutions is 0.5~5:100, silicate solutions are maintained at 75~80 DEG C, it will
Coupling agent is added drop-wise in silicate solutions, until after being added dropwise, is stirred 10~30 minutes, so that system is uniformly mixed, changed
Property silicate solutions；
3) preparation of composite modifier
The weight ratio 2~5 of modified Portland and phenol resin solution:10, by the phenol resin solution heating 40 of step 1)
~60 DEG C, the modified-silicate solution of step 2) is added under stiring, stirring obtains composite modifier in 30 minutes；
4) dipping is carried out to timber to be modified and be dried
(1) dipping modification is carried out to timber
Timber is put into the impregnating autoclave of sealing, vacuumize process is first carried out, composite modifier is then introduced, keeps simultaneously
Impregnating autoclave keeps certain temperature, then carries out pressurized treatments, by after a certain period of time, being that timber absorption the compound of certain mass changes
Property agent, the relative degree of vacuum of the vacuumize process is -0.095~-0.098MPa；The vacuumize process time is with impregnating autoclave
Volume change, at 30~120 minutes；The absolute pressure of the pressurized treatments is 1.0~2.5MPa；Pressurizing time is
1~4 hour, the temperature of impregnating autoclave was maintained at 30~40 DEG C；
(2) processing is dried to timber
Mode of the timber after impregnation through stacking is placed, it is 40%~70% that promoting the circulation of qi of going forward side by side, which is done to moisture content,；Again
Gas is done the timber for being 40%~70% to moisture content to be placed in dry kiln and be dried, is done under 50~70 DEG C of temperature condition
Dry 6~8 days；Then 2~3 days dry at 100~120 DEG C, it is 8% then to be dried at 130~140 DEG C to moisture content
~12% up to enhancing modified artificial forest wood finished product.
The phenol of the phenol resin solution, formaldehyde, aqueous slkali and water molar ratio be 1:2.2:0.4:4.2.
The weight ratio of the modified Portland and phenol resin solution is 4:10.
The coupling agent is N- (β-aminoethyl)-γ-aminopropyls front three (second) oxysilane (kh792), γ-aminopropyl
Triethoxysilane (kh550), γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes (kh560) or γ-(methacryls
Oxygen) propyl trimethoxy silicane (kh570) one or more.
The aqueous slkali is that mass percent concentration is 20%~40% sodium hydroxide or potassium hydroxide solution；
The mass percent concentration of the formaldehyde is 36.5%~37.2% formalin.
The silicate solutions are potassium silicate solution and/or sodium silicate solution.
The timber is artificial forest wood, and moisture content is less than 12%, and thickness is 8~20mm.
A kind of enhancing modified artificial forest wood tool prepared by enhancing modified artificial forest wood preparation method using the present invention
It has the following advantages：
1. fire-retardant anti-due to using silicate modified phenolic resin having as composite modifier improved wood, modified material
Rotten effect, density increase, and dimensional stability increases, and are especially different from the impact flexibility that other thermosetting resins reduce timber,
The impact flexibility for significantly improving timber has expanded its application range to make the utilization rate of modification material greatly improve；
2. the detection of (GB/T1927~1943-2009) " Physico-mechanical Properties of The Wood test method " according to national standards,
The physical and mechanical property of enhancing modified artificial forest wood prepared by the method for the present invention significantly improves, dimensionally stable, intensity height, corrosion resistant
It is fire-retardant, especially significantly improve enhancing modified artificial forest wood impact strength, impact strength 120.4~
150.2kJ/m2, increase rate 41.2%~52.2%.Enhancing modified artificial forest wood resist swollen rate (ASE) improve 50.1%~
60.7%；Deflection Modulus of Elasticity (MOE) has reached 11.5~16GPa, increase rate 35.1%~51.5%；Bending strength (MOR)
148.8~191.2MPa, increase rate 151.2%~212.8% are reached.
3. GB/T 17657-2013 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " environmental protection according to national standards
The burst size of methanal of performance detection, the enhancing modified artificial forest wood of preparation method of the present invention has reached 0.03~0.06mgm-3, compared with unmodified material and similar product, reduce obvious；
4. the artificial forest woods quality such as poplar is partially soft, when mechanical processing surface frequent occurrence burr, groove mark the defects of, it is modified
Wood surface is bright and clean after processing, and case hardness increases, and improves the machining property of artificial forest wood, innovation wood obviously
The hardness on the surface of material is 2~4 times of unmodified material, and is not had to post-production performance such as glue performance, top finishing performance
It adversely affects；
5. enhancing modified artificial forest wood flame retardant effect prepared by the method for the present invention is notable, enhance modified artificial forest wood
Oxygen index (OI) has reached 35%~55%, has reached GB8624-2012《Construction material and product burns grading performance》Middle defined
The B1 of resistance to combustion~A2 grades of requirement；
6. the enhancing modified artificial forest wood preparation method of the present invention, using inorganic-organic hybrid system as composite modifier,
While improving the mechanical property of enhancing modified artificial forest wood, it is especially apparent the anti-impact for improving enhancing modified artificial forest wood
Hit intensity, and the thermal stability and flame retardant property of enhancing modified artificial forest wood are improved simultaneously.The present invention enhances modifying artificial
Forest timber, impact strength increase rate 41.2%~52.2% resist swollen rate (ASE) to improve 28%~68%；Bending resistance springform
Measure (MOE) increase rate 35.1%~51.5%；Bending strength (MOR) increase rate 151.2%~212.8%；Carbon yield reaches
40%~50%；Oxygen index (OI) has reached 40%~60%.It can take into account simultaneously and save timber resources and with solid wooden floor board surface
The advantages that effect, burst size of methanal are less than unmodified material and similar product, can be widely used for indoor and outdoor.
Specific implementation mode
In order to advantageously promote the understanding of the technical characterstic to the present invention, below by conjunction with specific embodiments to this hair
Bright enhancing modified artificial forest wood is further described.It should be noted that embodiment is not to protect model to the present invention
The limitation enclosed.
The log scale for preparing enhancing modified artificial forest wood selects artificial forest wood, such as poplar, larch, pinus sylvestris var. mongolica, horse
Tail pine, China fir etc., the embodiment of the present invention is described in detail by taking poplar as an example.
A kind of enhancing modified artificial forest wood preparation method of embodiment 1, including the following contents：
1. modified-silicate solution
Prepare raw material according to following quality proportioning：
γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570)：The weight ratio of sodium silicate solution is 3:100.
2. prepared by modified sodium silicate
Sodium silicate solution is put into reaction kettle, is stirred, coupling agent is added drop-wise to silicic acid by heating in the case where temperature is 75 DEG C
In salting liquid, until after being added dropwise, stirs 20 minutes, so that system is uniformly mixed, obtain modified-silicate solution.
3. prepared by phenolic resin
1) it is 1 according to the molar ratio of following molar ratio ingredient phenol, formaldehyde, aqueous slkali and water:2.2:0.4:4.2；
2) phenol, aqueous slkali and water are put into successively in reaction kettle, is then heated to 40 DEG C, is slowly added to formaldehyde
The formaldehyde of total amount 80% heats up 85 DEG C, carries out first stage reaction, in 55 minutes reaction time, viscosity reaches 60mPas；
3) cool down 40 DEG C, the formaldehyde of formaldehyde total amount residue 20% is added, adds and is to slowly warm up to 90 DEG C, and at this temperature
Viscosity is measured by sampling and is cooled to 40 DEG C of blowings when viscosity reaches 120mPas.
4. prepared by composite modifier
1) mass ratio of phenol resin solution, water and modified sodium silicate solution is 10:3:10；
2) phenol resin solution is heated up 42 DEG C, is incorporated as the water of 30% mass of phenol resin solution under stiring, 20 points
Zhong Hou is added a concentration of 40% aqueous slkali of phenol resin solution 5%, then adds as phenol resin solution phase homogenous quantities
Modified-silicate solution.After stirring 30 minutes, you can obtain composite modifier；
3) according to GB/T14704-2006《Based Wood Adhesives and its resin method of inspection》Detect phenolic aldehyde prepared by embodiment 1
The quality performance indicators of resin solution, testing result are as shown in table 1.
5. timber pickling is handled
1) it is vacuum-treated
The poplar square bar for being 10% by moisture content, long 1250mm × wide 20mm × thickness 20mm are put into leaching using fixed frame
In stain process tank, vacuumize process then is carried out to process tank, the wherein relative pressure in process tank is -0.096MPa, vacuum
Time is 60min；
2) composite modifier is introduced
The temperature of tank body is heated to 40 DEG C, then imports composite modifier prepared by step 4 by way of negative pressure
Impregnation tank is pumped into the solution that timber in tank can be completely covered, then solves under conditions of the volume of calculation processing test specimen
Except vacuum state, make the inside and outside pressure balance of process tank；
3) pressure treating wood
Using air compressor to carrying out pressurized treatments in impregnating autoclave, absolute pressure in tank is made to be kept for 2.1MPa, time
Then remaining composite modifier is discharged and is weighed by 120min, rear pressure relief, obtain impregnation timber；
6. the modified material acidification of dipping
Impregnation timber is placed at room temperature into promoting the circulation of qi drying, the dry tack free of impregnation timber is made, then will
Processing material is put into acid solution, after being put into a period of time, is taken out.The wherein moisture content 60% of the dry impreg of gas, acid solution are grass
Acid solution, a concentration of 7%, the time in acid solution is 3h；
7. impregnation material is dried
1) gas dry-cure
It by the impregnation material after acidification by the way of stacking, is placed in and carries out predrying at room temperature, its moisture content is made to reach
To 60% or so；
2) heat drying
Gas is done in impregnation material immigration dry kiln and is dried, low temperature drying first, drying temperature is 60 DEG C, the time
For 168h；Then 105 DEG C are warming up to, dry 72h；Then it heats up again 130 DEG C, drying reaches 12% up to moisture content, is increased
Strong modification material.
8. " GB/T 1927~1943-2009 Physico-mechanical Properties of The Wood test method " detection process according to national standards
Material mechanics index of physics, testing result are shown in Table 2.
A kind of enhancing modified artificial forest wood preparation method of embodiment 2：
Prepared by phenol resin solution, in addition to first stage reaction phenol resin solution viscosity is 80mPas, terminal viscosity
For 180mPas, remaining is same as Example 1；
Prepared by composite modifier, in addition to γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570)：Sodium metasilicate is molten
The weight ratio of liquid is 2:100；The mass ratio of phenol resin solution, water and modified sodium silicate solution is 10:5:10, remaining and implementation
Example 1 is identical；
Timber pickling is dried, in addition to the time of vacuum processing is 90min, pressurizing time 150min, low temperature
Dry, drying temperature is 50 DEG C, time 168h；Then 105 DEG C are warming up to, dry 96h；Then heat up again 140 DEG C, remaining with
Embodiment 1 is identical；
According to GB/T14704-2006《Based Wood Adhesives and its resin method of inspection》It is molten to detect resin prepared by embodiment
The quality performance indicators of liquid, testing result is as shown in table 1,
" GB/T 1927~1943-2009 Physico-mechanical Properties of The Wood test method " detection process material according to national standards
Mechanics index of physics, testing result are shown in Table 2.
A kind of enhancing modified artificial forest wood preparation method of embodiment 3：
Prepared by phenol resin solution, in addition to first stage reaction phenol resin solution viscosity is 120mPas, terminal viscosity
For 210mPas, remaining is same as Example 1；
Prepared by composite modifier, in addition to γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570)：Sodium metasilicate is molten
The weight ratio of liquid is 4:100；The mass ratio of phenol resin solution, water and modified sodium silicate solution is 10:7:10, remaining and implementation
Example 1 is identical；
Timber pickling is dried, in addition to the time of vacuum processing is 120min, pressurizing time 120min, low temperature
Dry, drying temperature is 50 DEG C, time 168h；Then 115 DEG C are warming up to, dry 96h；Then heat up again 140 DEG C, remaining with
Embodiment 1 is identical；
According to GB/T14704-2006《Based Wood Adhesives and its resin method of inspection》It is molten to detect resin prepared by embodiment
The quality performance indicators of liquid, testing result is as shown in table 1,
" GB/T 1927~1943-2009 Physico-mechanical Properties of The Wood test method " detection process material according to national standards
Mechanics index of physics, testing result are shown in Table 2.
Embodiment 4
Prepared by phenol resin solution, in addition to first stage reaction phenol resin solution viscosity is 150mPas, terminal viscosity
For 300mPas, remaining is same as Example 1；
Prepared by composite modifier, in addition to γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570)：Sodium metasilicate is molten
The weight ratio of liquid is 3:100；The mass ratio of phenol resin solution, water and modified sodium silicate solution is 10:9:10, remaining and implementation
Example 1 is identical；
Timber pickling is dried, in addition to the time of vacuum processing is 60min, pressurizing time 150min, low temperature
Dry, drying temperature is 50 DEG C, time 192h；Then 105 DEG C are warming up to, dry 120h；Then it heats up again 140 DEG C, remaining
It is same as Example 1；
According to GB/T14704-2006《Based Wood Adhesives and its resin method of inspection》It is molten to detect resin prepared by embodiment
The quality performance indicators of liquid, testing result is as shown in table 1,
" GB/T 1927~1943-2009 Physico-mechanical Properties of The Wood test method " detection process material according to national standards
Mechanics index of physics, testing result are shown in Table 2.
The quality performance indicators testing result of 1 composite modifier of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Solid content (%) | 42.58 | 39.62 | 36.59 | 33.46 |
| Viscosity (mPas) | 16.8 | 17.4 | 18.9 | 19.6 |
| PH value | 11.5 | 11.3 | 11.2 | 11.4 |
| Free formaldehyde content (%) | 0.08 | 0.06 | 0.05 | 0.06 |
| Water mixing multiple | Arbitrarily | Arbitrarily | Arbitrarily | Arbitrarily |
| Storage period (4~30 DEG C) | 1 year | 1 year | 1 year | 1 year |
Table 2 enhances the performance test results of Modified Poplar timber
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 3 | Compare material | |
| Averag density (g/cm3) | 0.68 | 0.65 | 0.62 | 0.58 | 0.41 |
| Rate of body weight gain (%) | 56.12 | 50.68 | 46.72 | 41.48 | |
| Contract with dry rate (%) | 6.4 | 7.1 | 7.9 | 8.4 | 10.1 |
| Resist swollen rate (%) | 68 | 59 | 42 | 28 | |
| Deflection Modulus of Elasticity (GPa) | 15.7 | 13.6 | 12.4 | 11.5 | 9.2 |
| Bending strength (MPa) | 191.2 | 174.9 | 161.7 | 148.8 | 67.2 |
| Impact strength (kJ/m2) | 150.2 | 139.8 | 131.5 | 120.4 | 85.2 |
Testing result shows：
1. by the detection of standard GB/T/T1927~1943-2009 " Physico-mechanical Properties of The Wood test method ", this
The physical and mechanical property of Modified Poplar prepared by inventive method is significantly improved, and the contract with dry rate of Modified Poplar improves 16.8%
~36.6%, resist swollen rate to improve 28%~68%, Deflection Modulus of Elasticity improves 35.1%~51.5%, and bending strength improves
151.2%~212.8%, impact strength improves 41.2%~52.2%.
2. the averag density of enhancing modified artificial forest wood prepared by the method for the present invention increases, density improves 41.4%~
57.8%, rate of body weight gain has reached 41.4%~56.1%.
1 fire retardancy test of test example
" GB/T2406-2009 plastics measure burning behavior with oxygen index method " the test embodiment of the present invention according to national standards
The anti-flammability of 1-4, reference examples timber.Enhancing modified artificial forest wood, control timber prepared by 1-4 of the embodiment of the present invention is processed
At the model that specification is long 120mm × wide 10mm × thickness 10mm, after the burning of regulation testing time, oxygen is calculated as follows and is referred to
Number, determines resistance to combustion grade.
coOxygen concentration is indicated with volume fraction；VOAt -23 DEG C, the oxysome product of per unit area in mixed gas；
VNAt -23 DEG C, the volume of the nitrogen of per unit volume in mixed gas.
Test result is as shown in table 3
| Oxygen index (OI) (%) | Resistance to combustion grade | |
| Embodiment 1 | 48 | B1 (fire retardant) |
| Embodiment 2 | 41 | B1 (fire retardant) |
| Embodiment 3 | 38 | B1 (fire retardant) |
| Embodiment 4 | 34 | B1 (fire retardant) |
| Compare material | 21 | It is inflammable |
Testing result shows：
The oxygen index (OI) of enhancing modified artificial forest wood prepared by the method for the present invention is 34%~48%, is far above fire retardant timber
The value of oxygen index (OI) defined shows that the enhancing modified artificial forest wood prepared by the method for the present invention has reached the fire retardant rank marks of B1
It is accurate.
Claims (8)
1. a kind of enhancing modified artificial forest wood preparation method, characterized in that it include in have：The system of phenol resin solution
Standby, modified-silicate solution preparation, the preparation of composite modifier and carry out that dipping is modified to be changed with drying process to timber
Property artificial forest wood, specific preparation process are as follows：
1) preparation of phenol resin solution
Phenol, formaldehyde, aqueous slkali and water molar ratio be 1:2.0~2.4:0.2~0.6:4.0~4.5；By phenol, aqueous slkali
It is put into reaction kettle successively with water, is then heated to 40~45 DEG C, be slowly added to the formaldehyde of formaldehyde total amount 80%, heating 80
~85 DEG C, first stage reaction is carried out, in 50~60 minutes reaction time, obtains first stage reaction solution；The first rank will be obtained again
Section reaction solution cools down 40~50 DEG C, and the formaldehyde of formaldehyde total amount residue 20% is added, adds and is to slowly warm up to 90~92 DEG C, and herein
At a temperature of viscosity is measured by sampling, when viscosity reaches 40~300mPas, be cooled to 40 DEG C of blowings be made phenol resin solution；
2) preparation of modified-silicate solution
The weight ratio of coupling agent and silicate solutions is 0.5~5:100, silicate solutions are maintained at 75~80 DEG C, will be coupled
Agent is added drop-wise in silicate solutions, until after being added dropwise, is stirred 10~30 minutes, so that system is uniformly mixed, obtain modified silicon
Acid salt solution；
3) preparation of composite modifier
The weight ratio 2~5 of modified Portland and phenol resin solution:10, by the phenol resin solution heating 40~60 of step 1)
DEG C, the modified-silicate solution of step 2) is added under stiring, stirring obtains composite modifier in 30 minutes；
4) dipping is carried out to timber to be modified and be dried
(1) dipping modification is carried out to timber
Timber is put into the impregnating autoclave of sealing, vacuumize process is first carried out, then introduces composite modifier, while keeping impregnating
Tank keeps certain temperature, then carries out pressurized treatments, by after a certain period of time, being that timber absorbs the composite modified of certain mass
The relative degree of vacuum of agent, the vacuumize process is -0.095~-0.098MPa；The vacuumize process time is with impregnating autoclave
Volume change, at 30~120 minutes；The absolute pressure of the pressurized treatments is 1.0~2.5MPa；Pressurizing time is 1
~4 hours, the temperature of impregnating autoclave was maintained at 30~40 DEG C；
(2) processing is dried to timber
Mode of the timber after impregnation through stacking is placed, it is 40%~70% that promoting the circulation of qi of going forward side by side, which is done to moisture content,；Again by gas
It does the timber for being 40%~70% to moisture content to be placed in dry kiln and be dried, dry 6 under 50~70 DEG C of temperature condition
~8 days；Then dry 2~3 days at 100~120 DEG C, then dried at 130~140 DEG C to moisture content be 8%~
12% up to enhancing modified artificial forest wood finished product.
2. a kind of enhancing modified artificial forest wood preparation method according to claim 1, characterized in that the phenolic resin
The phenol of solution, formaldehyde, aqueous slkali and water molar ratio be 1:2.2:0.4:4.2.
3. a kind of enhancing modified artificial forest wood preparation method according to claim 1 or 2, characterized in that the modification
The weight ratio of silicate and phenol resin solution is 4:10.
4. a kind of enhancing modified artificial forest wood preparation method according to claim 1, characterized in that the coupling agent is
N- (β-aminoethyl)-γ-aminopropyls front three (second) oxysilane (kh792), gamma-aminopropyl-triethoxy-silane (kh550),
γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes (kh560) or γ-(methacryloxypropyl) propyl trimethoxy silicane
(kh570) one or more of.
5. a kind of enhancing modified artificial forest wood preparation method according to claim 2, characterized in that the aqueous slkali is
Mass percent concentration is 20%~40% sodium hydroxide or potassium hydroxide solution.
6. a kind of enhancing modified artificial forest wood preparation method according to claim 2, characterized in that the matter of the formaldehyde
Amount percent concentration is 36.5%~37.2% formalin.
7. a kind of enhancing modified artificial forest wood preparation method according to claim 1, characterized in that the silicate is molten
Liquid is potassium silicate solution and/or sodium silicate solution.
8. a kind of enhancing modified artificial forest wood preparation method according to claim 1, characterized in that the timber is
Artificial forest wood, moisture content are less than 12%, and thickness is 8~20mm.
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