CN107599093A - A kind of water ballast functional form Wood modifier and its processing method - Google Patents
A kind of water ballast functional form Wood modifier and its processing method Download PDFInfo
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Abstract
The present invention relates to a kind of water ballast functional form Wood modifier and its processing method, wherein water ballast functional form Wood modifier is made up of the component of following parts by weight：100 parts of phenol, 100 ~ 150 parts of formaldehyde, 80 ~ 150 parts of hydroxymethyl-2 dihydroxy-ethylene urea, 10 ~ 30 parts of hydroxymethyl-2 dihydroxy-ethylene urea catalyst, 30 ~ 50 parts of Ludox, 25 ~ 35 parts of sodium hydroxide solution, 20 ~ 40 parts of hydrochloric acid solution.Advantage：1）Synthesis technique is simply easily operated；2）Modifier molecules amount is low, high treating effect；3）Wood dimensional stability is significantly improved, density of wood is big after modified, intensity is high, antiseptic fire-retardation, processing characteristics are good, can be widely used for floor, solid wood door and window, furniture, house decorative material etc., while can be additionally used in the outdoor architectures such as wooden footway, wayside pavilion.
Description
Technical field
The present invention relates to a kind of water ballast functional form Wood modifier and its processing method, belongs to wood processing technique neck
Domain.
Background technology
China is world's second largest lumber consumption state and the first summer wood importer, nearly 5 billion cubic meter of Year's consumption（Including
Log, artificial board etc.）.According to 2015《China's Forestry Development is reported》It has been shown that, China's timber resources supply external dependence degree reach
50%, exceed warning line, with attention of the countries in the world to environmental protection, imported timber will be fewer and fewer.In March, 2016 state
Year, forest pathogen was 25403.6 ten thousand steres during business institute reply national " 13 ", compared to decline during " 12 "
Nearly 7%.It can be seen that the contradiction of the effective supply of China's timber resources and ever-increasing social demand is increasingly prominent.It is complete according to the 8th time
State's forest assessment result is shown, 0.69 hundred million hectares of China's artificial forest area, is occupied first place in the world.Therefore, greatly develop artificial
Woods, it is to solve with the wildwood timber and the high-quality timber resources of import of artificial forest wood substitution of resources China total amount wretched insufficiency
China's wood supply problem, realize the effective way of wood utilization sustainable development.But artificial forest wood is present, and density is small, material
Matter is soft, low intensity, it is apt to rot, inflammable the defects of, limit its application in construction material and Furniture manufacture etc., therefore,
Artificial forest material grade is improved, realizes that its increment utilizes, it is necessary to which functionality improvement is carried out to it.
Wooden modifying using the method processing timber of physically or chemically or both dual-purpose, improves wood performance, assigned simultaneously more
Give the function that timber is new.Chemical modification be artificial forest wood be modified Main Means, resin dipping improved wood be at present more
Successfully industrialization method for modifying wood, but improved wood is impregnated from conventional Lauxite, phenolic resin, furfuryl alcohol resin etc.,
The problems such as single, the modified decoction molecular weight of improved wood functionalization bigger than normal, environmental pollution, high integrated cost be present.Therefore, research and develop
Low molecule amount, low content of free formaldehyde content, the composite multifunction type Wooden modifying medicament of low cost turn into current study hotspot.
Phenolic resin has the characteristics that water-fast, weather-proof, wearability, and it has than Lauxite anti-shrinkage efficiency and ageing-resistant performance
Good, than furfuryl alcohol resin, chemical agent loses the advantages of small in the drying process.In this professional skill field, disclosed and phenol
The related organic/inorganic composite wood modifying agent Patents technology of urea formaldehyde has：
Patent CN201310421156.2 " a kind of Phenolic resin wood adhesive modifying agent and its application " discloses a kind of wooden bamboo
Material impregnating phenolic resin is modified adhesive, including：Phenolic resin adhesive and its modifying agent（The 0-50 parts of polyvinyl alcohol 1788,
Silicon dioxide granule 1-12 parts, TiO 2 particles 1-12 parts, PVP K30 0.1-5 parts, non-ionic surface
Activating agent APES 0.1-1.5 parts）By 1:1-8 is mixed, and modifying agent is made.The medicament selects phenolic resin gluing
Agent is host, and it is larger greatly modifier molecules amount to be present, osmotic evenness problem.
Patent CN201510344965.7 " a kind of Nanometer Copper modified low molecular weight phenolic resin and preparation method thereof " is open
A kind of timber pickling phenolic resin modified dose of preparation method of Nanometer Copper modified low molecular weight, main decoction include phenol, sulphur
Sour copper mixed solution（Copper sulphate, disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, sodium hydroxide）, formaldehyde mixed solution（First
The aldehyde aqueous solution, sodium pyrophosphate, sodium potassium tartrate tetrahydrate）, sodium hydrate aqueous solution.In the same of synthesizing water-solubility pf resin of low molecular weight
When fabricated in situ Nanometer Copper, it includes prepolymerization, fabricated in situ Nanometer Copper and polymerisation again.The medicament improved wood mechanical property
Energy, dimensional stability and durability are improved, but synthesis technique is more complicated, integrated cost is higher.
Patent CN201410308703.0 " a kind of preparation method and application of multi-functional timber dip resin modifying agent "
Using phenol, formaldehyde, melamine, urea as host, using boric acid and Firebrake ZB as feature host, while a certain amount of one is added
Contracting DPG, synthesis is a kind of to have weightening enhancing, fire-retardant and anti-corrosion function low alkalinity multicomponent copolycondensation modifier concurrently；
Patent CN201510001987.3 " be suitable to the preparation technology of phenol-formaldehyde resin modified that Wood construction lifts with material anti-flaming function and
Application method " is disposably fed intake using phenol, formaldehyde as host, and boric acid is added in building-up process, and one kind, which is made, has excellent flame
The phenol-formaldehyde resin modified medicament of function.Boron compound has a good anti-flammability, but this kind of inorganic combustion inhibitor hygroscopicity it is strong and
Easily it is lost in.
The content of the invention
Proposed by the present invention is a kind of water ballast functional form Wood modifier and its modification processing method, and the purpose is to overcome mesh
Preceding Wood modifier study hotspot and existing above mentioned problem, abundant, uniformly penetrating is carried out to artificial forest wood, significantly improves wood
The dimensional stability and physical and mechanical property of material, while wood preservation, fire resistance are assigned, free formaldehyde content is low, environment friend
It is good.
The technical solution of the present invention, a kind of water ballast functional form Wood modifier, is made up of the component of following parts by weight：
100 parts of phenol, 100 ~ 150 parts of formaldehyde, 80 ~ 150 parts of hydroxymethyl-2 dihydroxy-ethylene urea, hydroxymethyl-2 dihydroxy-ethylene urea catalysis
10 ~ 30 parts of agent, 30 ~ 50 parts of Ludox, 25 ~ 35 parts of sodium hydroxide solution, 20 ~ 40 parts of hydrochloric acid solution.
The modifying agent synthesizes as follows：
1. phenol and mass percent concentration are added in reactor for 37% formalin, heating, stirring, and control temperature
Scope adjusts solution ph to 9.0 ~ 10.0 between 40 ~ 45 DEG C, with the sodium hydroxide solution of concentration 30%；
2. because phenol and formaldehyde reaction are exothermic reaction, mixeding liquid temperature is rapidly increased to 75 ~ 85 DEG C, controlling reaction temperature, protected
Hold 60 ~ 90 minutes；
3. adjusting mixed solution pH to 8.0 ~ 9.0 with the hydrochloric acid solution of concentration 20%, cooling down is to 30 ~ 40 DEG C, in the feelings of stirring
Continue reaction under condition 20 ~ 30 minutes, obtain hydroxymethyl phenol monomer solution；
4. by obtained hydroxymethyl phenol monomer solution, hydroxymethyl-2 dihydroxy-ethylene urea, silicon that solids content is 10%-45% are added
Colloidal sol, magnetic agitation 10 ~ 20 minutes under the conditions of room temperature after mixing；
5. hydroxymethyl-2 dihydroxy-ethylene urea catalyst is added, with the hydrochloric acid solution of concentration 20% regulation pH of mixed to 7.5 ~ 8, magnetic
Power stir 10 ~ 15 minutes it is uniform to solution, that is, obtain a kind of water ballast functional form modifying agent.
A kind of processing method of artificial forest wood water ballast functional form modifying agent, comprises the following steps：
1. being diluted the modifying agent prepared with water, it is adjusted to require concentration, it is standby；
2. the artificial forest wood that moisture content is 10% or less is fitted into closed impregnation tank, vacuumizing makes negative pressure in tank
For -0.08 ~ -0.01MPa, kept for 45 ~ 60 minutes；
3. modifying agent decoction is injected into process tank using the suction function in impregnation tank and floods timber, vacuum is released, is entered
The laddering pressurization of row, pressurize 0.1 ~ 0.2MPa every time, is kept for 10 ~ 20 minutes, repeated 5 ~ 15 times, to 0.8 ~ 1.5MPa of application
Air pressure, keep 4 ~ 6 hours；
4. releasing the pressure of impregnation tank, remaining modifying agent is discharged, takes out the timber of impregnation, carries out kiln drying, extremely
Moisture content 8 ~ 12%.
The invention has the advantages that
1）The hydroxymethyl phenol activated monomer mainly generated by phenol and formaldehyde reaction, such as a hydroxymethyl phenol, dihydroxymethyl phenol,
Same hydroxymethyl-2 dihydroxy-ethylene urea, Ludox are mixed to form stable sol system solution, after impregnated timber, are heating and curing
For journey with forming polymer by Covalent bonding together in wood cell wall and lumen, synthesis technique is simply easily operated；
2）Modifier molecules amount is low, is easy to uniformly penetrating timber, high treating effect；
3）Monomer reactivity functional group easily reacts with wood cell wall hydroxyl in modifying agent, so as to be fixed on wood cell wall
In, significantly improve wood dimensional stability, and artificial forest wood after modified, have density is big, intensity is high, anti-corrosion, resistance
Performance is fired, processing characteristics is good, produces the advantages that environmentally friendly；
4）Timber after modification can be widely used for floor, solid wood door and window, furniture, house decorative material etc., while also can use
In outdoor architectures such as wooden footway, wayside pavilions, artificial forest wood application is extended.
Embodiment
Embodiment 1
The process of synthetically prepared water ballast functional form Wood modifier, comprises the following steps：
1. the formalin that 100 parts of phenol and 120 parts of mass percent concentrations are 37% is added in reactor, heating, stirring,
And controlling reaction temperature is 40 DEG C, pH value is adjusted to 9.0 with concentration 30%NaOH solution；
2. because phenol and formaldehyde reaction are exothermic reaction, mixeding liquid temperature is rapidly increased to 75 DEG C, controlling reaction temperature, keeps 70
Minute；
3. adjusting pH value of solution to 8.0 with the hydrochloric acid solution of concentration 20%, cooling down continues to react to 30 DEG C in the case of stirring
25 minutes, obtain hydroxymethyl phenol monomer solution；
4. by obtained hydroxymethyl phenol monomer solution, it is molten to add hydroxymethyl-2 dihydroxy-ethylene urea, silicon that solids content is 25%
Glue, magnetic agitation 20 minutes under the conditions of room temperature after mixing；
5. adding hydroxymethyl-2 dihydroxy-ethylene urea catalyst, pH value of solution is adjusted to 7.5 with the hydrochloric acid solution of concentration 20%, magnetic force stirs
Mix, discharging uniform to solution in 15 minutes.
The processing method of Cunninghamia lanceolata water ballast functional form modifying agent, comprises the following steps：
1. the modifying agent prepared is diluted with water, it is standby to modifier solution mass fraction 20%；
2. Cunninghamia lanceolata of the 1000mm × 200mm × 25mm specifications moisture content less than 10% is loaded at closed dipping
Manage in tank, vacuumizing makes negative pressure in tank be -0.09MPa, is kept for 45 minutes；
3. modifying agent decoction is injected into process tank using the suction function in impregnation tank and floods timber, vacuum is released, is entered
The laddering pressurization of row, pressurize 0.2MPa every time, is kept for 20 minutes, repeated 6 times, small to the air pressure for applying 1.2MPa, holding 6
When；
4. releasing the pressure of impregnation tank, remaining modifying agent is discharged, takes out the timber of impregnation, carries out kiln drying, extremely
Moisture content 12%, obtains improved wood.
According to 1927 ~ 1943-2009 of GB/T《Physico-mechanical Properties of The Wood test method》Deng standard method to Wooden modifying
Every physical and mechanical property indexs before and after the processing are detected, as a result as follows：Timber rate of body weight gain is up to 34% after processing, moisture content
10%, density is by before processing 0.348g/cm3Increase to 0.611g/cm3；Anti- swollen rate improves more than 56%；Deflection Modulus of Elasticity by
4.9GPa increases to 7.3GPa；Bending strength increases to 81.2MPa by 46.8MPa；Case hardness increases to 2510N by 1014N.
According to GB 18580-2001《Form aldehyde release is limited the quantity in indoor decorating and refurnishing materials, wood-based plate and its product》In do
The dry modified China fir burst size of methanal of device method test, test value are less than 0.45mg/L.
According to GB/T 2406.2-2009《Plastics determine burning behavior with oxygen index method》Test before and after China fir modification
Oxygen index (OI), as a result for：Oxygen index (OI) brings up to 43% by before processing 23%.
According to GB/T 13942.1-2009《Durability of wood energy, part 1：Natural decay resistance laboratory test methods》
Measure China fir antiseptic property before and after the processing, as a result for：China fir is modified weight-loss ratio of the material after domestomycetes is rotten after material and processing
Respectively 65.9% and 10.5%, China fir corrosion resistant performance improves after showing modification.
Embodiment 2
The synthesis technique of water ballast functional form Wood modifier is prepared, is comprised the following steps：
1. the formalin that 100 parts of phenol and 130 parts of mass percent concentrations are 37% is added in reactor, heating, stirring,
And controlling reaction temperature is 40 DEG C, pH value is adjusted to 9.0 with concentration 30%NaOH solution；
2. because phenol and formaldehyde reaction are exothermic reaction, mixeding liquid temperature is rapidly increased to 80 DEG C, controlling reaction temperature, keeps 60
Minute；
3. with the hydrochloric acid conditioning solution pH to 8.0 of concentration 20%, cooling down continues 30 points of reaction to 30 DEG C in the case of stirring
Clock, obtain hydroxymethyl phenol monomer solution；
4. by obtained hydroxymethyl phenol monomer solution, it is molten to add hydroxymethyl-2 dihydroxy-ethylene urea, silicon that solids content is 30%
Glue, magnetic agitation 20 minutes under the conditions of room temperature after mixing；
5. hydroxymethyl-2 dihydroxy-ethylene urea catalyst is added, with the hydrochloric acid conditioning solution pH to 7.5 of concentration 20%, magnetic agitation 15
Minute is uniform to solution, discharging.
The processing method of Poplar wood in plantation water ballast functional form modifying agent, comprises the following steps：
1. the modifying agent prepared is diluted with water, it is standby to modifier solution mass fraction 20%；
2. Poplar wood in plantation of the 1000mm × 200mm × 25mm specifications moisture content less than 10% is loaded at closed dipping
Manage in tank, vacuumizing makes negative pressure in tank be -0.09MPa, is kept for 40 minutes；
3. modifying agent decoction is injected into process tank using the suction function in impregnation tank and floods timber, vacuum is released, is entered
The laddering pressurization of row, pressurize 0.2MPa every time, is kept for 20 minutes, repeated 5 times, small to the air pressure for applying 1.0MPa, holding 4
When；
4. releasing the pressure of impregnation tank, remaining modifying agent is discharged, takes out the timber of impregnation, carries out kiln drying, extremely
Moisture content 12%, obtains improved wood.
According to 1927 ~ 1943-2009 of GB/T《Physico-mechanical Properties of The Wood test method》Deng standard method to modifying cotton wood
Every physical and mechanical property indexs before and after the processing are detected, as a result as follows：Timber rate of body weight gain is up to 37% after processing, moisture content
8%, density is by before processing 0.389g/cm3Increase to 0.691g/cm3；Anti- swollen rate improves more than 57%；Deflection Modulus of Elasticity by
7.9GPa increases to 13.6GPa；Bending strength increases to 122.7MPa by 57.2MPa；Case hardness is increased to by 1130N
3210N。
According to GB 18580-2001《Form aldehyde release is limited the quantity in indoor decorating and refurnishing materials, wood-based plate and its product》In do
The dry modified China fir burst size of methanal of device method test, test value are less than 0.40mg/L.
According to GB/T 2406.2-2009《Plastics determine burning behavior with oxygen index method》Test before and after China fir modification
Oxygen index (OI), as a result for：Oxygen index (OI) brings up to 49% by before processing 21%.
According to GB/T 13942.1-2009《Durability of wood energy, part 1：Natural decay resistance laboratory test methods》
Measure poplar antiseptic property before and after the processing, as a result for：Weight-loss ratio of the modifying cotton wood material after domestomycetes is rotten after material and processing
Respectively 59.6% and 8.9%, poplar corrosion resistant performance improves after showing modification.
Claims (2)
- A kind of 1. water ballast functional form Wood modifier, it is characterized in that component forming by following parts by weight：100 parts of phenol, formaldehyde 100 ~ 150 parts, 80 ~ 150 parts of hydroxymethyl-2 dihydroxy-ethylene urea, 10 ~ 30 parts of hydroxymethyl-2 dihydroxy-ethylene urea catalyst, silicon is molten 30 ~ 50 parts of glue, 25 ~ 35 parts of sodium hydroxide solution, 20 ~ 40 parts of hydrochloric acid solution；The synthetic method of the modifying agent, including it is as follows：1. phenol and mass percent concentration are added in reactor for 37% formalin, heating, stirring, and control temperature Scope adjusts solution ph to 9.0 ~ 10.0 between 40 ~ 45 DEG C, with the sodium hydroxide solution of concentration 30%；2. because phenol and formaldehyde reaction are exothermic reaction, mixeding liquid temperature is rapidly increased to 75 ~ 85 DEG C, controlling reaction temperature, protected Hold 60 ~ 90 minutes；3. adjusting mixed solution pH to 8.0 ~ 9.0 with the hydrochloric acid solution of concentration 20%, cooling down is to 30 ~ 40 DEG C, in the feelings of stirring Continue reaction under condition 20 ~ 30 minutes, obtain hydroxymethyl phenol monomer solution；4. by obtained hydroxymethyl phenol monomer solution, hydroxymethyl-2 dihydroxy-ethylene urea, silicon that solids content is 10%-45% are added Colloidal sol, magnetic agitation 10 ~ 20 minutes under the conditions of room temperature after mixing；5. hydroxymethyl-2 dihydroxy-ethylene urea catalyst is added, with the hydrochloric acid solution of concentration 20% regulation pH of mixed to 7.5 ~ 8, magnetic Power stir 10 ~ 15 minutes it is uniform to solution, that is, obtain a kind of water ballast functional form modifying agent.
- 2. a kind of processing method of water ballast functional form Wood modifier for artificial forest wood, its spy comprise the following steps：1. being diluted the modifying agent prepared with water, it is adjusted to require concentration, it is standby；2. the artificial forest wood that moisture content is 10% or less is fitted into closed impregnation tank, vacuumizing makes negative pressure in tank For -0.08 ~ -0.01MPa, kept for 45 ~ 60 minutes；3. modifying agent decoction is injected into process tank using the suction function in impregnation tank and floods timber, vacuum is released, is entered The laddering pressurization of row, pressurize 0.1 ~ 0.2MPa every time, is kept for 10 ~ 20 minutes, repeated 5 ~ 15 times, to 0.8 ~ 1.5MPa of application Air pressure, keep 4 ~ 6 hours；4. releasing the pressure of impregnation tank, remaining modifying agent is discharged, takes out the timber of impregnation, carries out kiln drying, extremely Moisture content 8 ~ 12%；Described artificial forest wood is mainly poplar, China fir, pine, Eucalyptus, rubber wood timber.
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Cited By (4)
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| CN110787955A (en) * | 2019-09-17 | 2020-02-14 | 陈秉鸿 | Vacuum infusion process for solid wood |
| CN113400428A (en) * | 2021-06-10 | 2021-09-17 | 广东省林业科学研究院 | Method for enhancing corrosion resistance and termite resistance of wood by using nano zinc oxide |
| CN113510811A (en) * | 2021-04-30 | 2021-10-19 | 中南林业科技大学 | Method for reinforcing poplar wood by compounding 2D resin and sodium silicate |
| CN114213573A (en) * | 2021-12-17 | 2022-03-22 | 中国林业科学研究院木材工业研究所 | Acrylic ester microemulsion wood modifier and preparation method and application thereof |
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