The synthetic method of Lauxite precipitation and answering as amino resin adhesive modifying agent thereof
With
Technical field
The present invention relates to the synthetic method of a kind of Lauxite precipitation and improve as amino resin adhesive
The application of agent, belongs to adhesive of artificial board and manufactures field.
Background technology
Amino resin adhesive is the adhesive that timber industry consumption is maximum, accounts for the 90% of Wood-based Panel Production glue consumption
Above, can't be replaced by other adhesive so far due to its cost advantage.The amino resins that prior art produces
Adhesive, greatest problem is that resistance to water especially heat-proof water performance is strong, additionally, due to formula present in use
Deficiency in design, the burst size of methanal of cementitious article is relatively big, annoyings the production of timber industry and artificial always
The use of plate end user.
To add carbamide by several times, the method synthesis urea-formaldehyde resin adhesive reducing Final molar ratio is to solve burst size of methanal
One of effective ways;It is another with urea-melamine-formaldehyde ternary polymerization mode synthetic amino resin adhesive
A kind of method of effective reduction burst size of methanal.It is unfavorable that amino resin adhesive also can be caused by above method simultaneously
Impact, as storage stability declines, bonding strength declines, resistance to water reduction etc..With nanometer particle-modified amino
Resin adhesive is little based on nano particle diameter, and specific surface area is big, and surface can be high, and a large amount of insatiable hunger is contained on surface
And residual bond, reactivity is high, and has the strongest interaction even respond between amino resin adhesive, no
Only can reduce the burst size of methanal of amino resin adhesive, it is also possible to improve bonding strength.Chinese patent literature
CN101818036A discloses a kind of method of silicate nano-clay modified urea-formaldehyde resin adhesive;China is specially
Profit document CN 102276734A discloses the side of the cellulose modified urea-formaldehyde resin adhesive of a kind of nanocrystal
Method;Chinese patent literature CN101696348B discloses a kind of gluing with nano-titanium dioxide modified Lauxite
The method of agent;Chinese patent literature CN 101747853B discloses a kind of organic amine composite Nano zirconium phosphate and changes
The method of property urea-formaldehyde resin adhesive;Chinese patent literature CN 101880437A discloses a kind of employing nanometer
The method of the modified urea-formaldehyde resin adhesives such as titanium dioxide, nano silicon, nano-calcium carbonate;Chinese patent
Document CN 103275660A discloses a kind of method using carbon nano-tube modification urea-formaldehyde resin adhesive.But
Above method all uses inorganic nano material, and the preparation method of relevant nano material is complex, and price is more
Costliness, causes modified high cost, is not suitable with the manufacturing present situation of wood-based panel industry low cost.
Chinese patent literature CN102898664A discloses the preparation method of a kind of urea formaldehyde resin microsphere, (1)
Preparing Lauxite prepolymer: add water, dispersant in the reactor, stirring and dissolving is uniform, add carbamide,
Formaldehyde, uses alkaline matter to adjust pH value to alkalescence;Then be heated to 40~90 DEG C, polyreaction 0.5~
5 hours, obtain Lauxite prepolymer;(2) resin solidification liquid is prepared: in another reactor, add water, consolidate
Agent, stirring and dissolving is uniform, is warming up to 40~70 DEG C, obtains the resin solidification liquid that pH value is 0.1-3.0;(3)
Lauxite prepolymer temperature is adjusted to 40~70 DEG C, then uses dropping equipment uniformly to instill resin solidification liquid
In carry out curing reaction;After reaction terminates, then it is neutralized, filters, obtain urea formaldehyde resin microsphere;Described step
(1) formaldehyde in is solid formaldehyde or/and liquid formaldehyde solution;Carbamide is 1-2:1 with the mol ratio of formaldehyde.
Obtain the urea formaldehyde resin microsphere in terms of structure and size with the highest homogeneity.
Chinese patent literature CN102993393A disclose a kind of synthesize uniform grading distribution Lauxite micro-
The method of ball, prepares Lauxite precipitation by adding surfactant, carbamide and formaldehyde in distilled water
After, sucking filtration washing obtain urea formaldehyde resin microsphere, and formaldehyde is 2:1 with the mol ratio of carbamide, gained precipitate
Microscopic appearance be spherical, can be used for chromatograph packing material, catalyst carrier, binding agent, super capacitor material and ring
Environment pollution process aspect.
Summary of the invention
It is an object of the invention to provide the synthesis side that a kind of manufacture method simplifies, the Lauxite of low cost precipitates
Method.
For reaching goal of the invention, the technical solution used in the present invention is: the synthetic method of a kind of Lauxite precipitation,
The steps include:
(1) formalin strong acid is transferred to pH value 1-5;Concentration of formaldehyde 35-38%;
(1) formaldehyde/urea=0.5-1 in molar ratio, is added into carbamide in formalin;
(2) 30-90 DEG C, react under stirring condition, continue stirring reaction when white cloud muddiness occurs
1-3h, is then down to room temperature and obtains Lauxite precipitation solution;
(3) being homogenized process through ultrasonic vibration by the Lauxite precipitation solution obtained, the process time is
15-120min, ultrasonic power 1000-1500W;
(4) Lauxite precipitation solution sucking filtration is obtained Lauxite precipitate and be washed to neutrality, at 30-70 DEG C
Under the conditions of be dried to constant weight.
Preferably, described strong acid is selected from sulphuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid or dicarboxylic acids.
Formaldehyde is reacted under the conditions of strong acid, low mole prop0rtion by the present invention with carbamide, is not required to use surface activity
Agent, is also not required to add firming agent or other materials, sonicated after, the Lauxite obtained be precipitated as micron,
Nano grade, its surface topography presents flakey, merges ball, spherical, floss ball, floss fusion ball and lamella
Fiber mixed structure etc..
The invention also discloses the Lauxite that said method obtains to precipitate as amino resin adhesive modifying agent
Application.
The method of this application is: Lauxite precipitation is added to by a certain percentage in amino resin adhesive, stirs
Mixing uniformly, the mass ratio of interpolation is amino resin adhesive: Lauxite precipitation=100:5-30.
Preferably, described amino resin adhesive is urea-formaldehyde resin adhesive, melamine formaldehyde resin adhesives
Or urea-melamine-formaldehyde terpolymer resin adhesive.
Preferably, add before Lauxite precipitates first by the urea-formaldehyde resin adhesive in amino resin adhesive or urine
The pH value of element-carbamide terpolymer resin adhesive is adjusted to 4.5, and melamine-formaldehyde resin adhesive glues
The pH value of agent does not adjusts.
The Lauxite precipitation that the synthetic method of the Lauxite precipitation of the present invention obtains adds amino resin adhesive to
Stick, is greatly improved bonding strength, reduces burst size of methanal, and does not change current wood-based panel industry amino resins
The use process conditions of adhesive, after adding Lauxite precipitation, amino resin adhesive is still with existing applying glue side
Formula and resin added applying glue, produce wood-based plate with existing Wood-based Panel Production method.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of the Lauxite precipitation of the embodiment of the present invention 1 synthesis.
Fig. 2 is the SEM photograph of the Lauxite precipitation of the 2-in-1 one-tenth of the embodiment of the present invention.
Fig. 3 is the SEM photograph of the Lauxite precipitation of the embodiment of the present invention 3 synthesis.
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is further elaborated.
Detailed description of the invention
Embodiment 1
(1) with hydrochloric acid, formalin pH that concentration is 35% is adjusted to 2;
(2) formaldehyde/urea=0.6 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) 45 DEG C, react under stirring condition, continue stirring reaction when white cloud muddiness occurs
2h, is then down to room temperature and obtains Lauxite precipitation solution;
(4) being homogenized process through ultrasonic vibration by the Lauxite precipitation solution obtained, the process time is
120min;Ultrasonic power 1000W;
(5) Lauxite precipitation solution sucking filtration is obtained Lauxite precipitate and be washed to neutrality, at 40 DEG C of bars
It is dried to constant weight under part.
The particle size range of the Lauxite precipitation obtained is 500nm-1 μm, and its configuration of surface is shown in Fig. 1.
Embodiment 2
(1) with sulphuric acid, formalin pH that concentration is 38% is adjusted to 1;
(2) formaldehyde/urea=0.5 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) 30 DEG C, react under stirring condition, continue stirring reaction when white cloud muddiness occurs
1h, is then down to room temperature and obtains Lauxite precipitation solution;
(4) being homogenized process through ultrasonic vibration by the Lauxite precipitation solution obtained, the process time is
20min;Ultrasonic power 1200W;
(5) Lauxite precipitation solution sucking filtration is obtained Lauxite precipitate and be washed to neutrality, at 30 DEG C of bars
It is dried to constant weight under part.
The particle size range of the Lauxite precipitation obtained is 800nm-1 μm, and its configuration of surface is shown in Fig. 2.
Embodiment 3
(1) with adipic acid, formalin pH that concentration is 36% is adjusted to 5;
(2) formaldehyde/urea=1 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) 90 DEG C, react under stirring condition, continue stirring reaction when white cloud muddiness occurs
3h, is then down to room temperature and obtains Lauxite precipitation solution;
(4) being homogenized process through ultrasonic vibration by the Lauxite precipitation solution obtained, the process time is
15min, ultrasonic power 1500W;
(5) Lauxite precipitation solution sucking filtration is obtained Lauxite precipitate and be washed to neutrality, at 70 DEG C of bars
It is dried to constant weight under part.
The particle size range of the Lauxite precipitation obtained is 1-10 μm, and its configuration of surface is shown in Fig. 3.
Comparative example 1
Commercially available E2 grade urea-formaldehyde resin adhesive, common melamine formaldehyde resin adhesives and E2 level carbamide-three
Paracyanogen amine-for-aldehyde ternary polymerization adhesive precipitates without Lauxite, by urea-formaldehyde resin adhesive and carbamide-
Carbamide ternary polymerization adhesive adjusts pH value=4.5 with 20% formic acid.Plywood is 5 layers of poplar group
Base, resin added 240g/m2(two-sided applying glue), hot pressing temperature 115 DEG C, hot pressing time 1min/mm, heat
Pressure unit pressure 1MPa;Particieboard is Aspen wood shavings, designs density 0.65g/cm3, thickness 8mm, executes
Glue amount 110kg/m3, hot pressing temperature 185 DEG C, hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa;
Fibre board for aspen fibers by using silicon, design density 0.9g/cm3, thickness 9mm, resin added 120kg/m3,
Hot pressing temperature 200 DEG C, hot pressing time 1min/mm, hot pressing unit pressure 4MPa.
Embodiment 4
Lauxite precipitation embodiment 1 obtained is separately added into commercially available E2 grade urea-formaldehyde resin adhesive, common
In melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde ternary polymerization adhesive, add
Before Lauxite precipitation, urea-formaldehyde resin adhesive and urea-melamine-formaldehyde ternary polymerization adhesive are used
20% formic acid adjusts pH value=4.5.Plywood is 5 layers of poplar assembly, resin added 240g/m2(two-sided applying glue),
Hot pressing temperature 115 DEG C, hot pressing time 1min/mm, hot pressing unit pressure 1MPa;Particieboard is poplar plane
Flower, designs density 0.65g/cm3, thickness 8mm, resin added 110kg/m3, hot pressing temperature 185 DEG C,
Hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa;Fibre board for aspen fibers by using silicon, design density
0.9g/cm3, thickness 9mm, resin added 120kg/m3, hot pressing temperature 200 DEG C, hot pressing time
1min/mm, hot pressing unit pressure 4MPa.
Lauxite precipitation improves the wood-based plate quality index result of amino resin adhesive and without urea aldehyde tree
The amine resin wood-based plate quality index Comparative result of fat precipitation is shown in Table 1, and wherein detection method is according to GB/T
17657-2013 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " is carried out.
Table 1, the embodiment 4 Lauxite precipitation improvement proportioning of amino resin adhesive and testing result and comparative example 1
Testing result
Embodiment 5
Lauxite precipitation embodiment 2 obtained is separately added into commercially available E2 grade urea-formaldehyde resin adhesive, common
In melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde ternary polymerization adhesive, add
Before Lauxite precipitation, urea-formaldehyde resin adhesive and urea-melamine-formaldehyde ternary polymerization adhesive are used
20% formic acid adjusts pH value=4.5.Plywood is 5 layers of poplar assembly, resin added 240g/m2(two-sided applying glue),
Hot pressing temperature 115 DEG C, hot pressing time 1min/mm, hot pressing unit pressure 1MPa;Particieboard is poplar plane
Flower, designs density 0.65g/cm3, thickness 8mm, resin added 110kg/m3, hot pressing temperature 185 DEG C,
Hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa;Fibre board for aspen fibers by using silicon, design density
0.9g/cm3, thickness 9mm, resin added 120kg/m3, hot pressing temperature 200 DEG C, hot pressing time
1min/mm, hot pressing unit pressure 4MPa.
Lauxite precipitation improves the wood-based plate quality index result of amino resin adhesive and without urea aldehyde tree
The amine resin wood-based plate quality index Comparative result of fat precipitation is shown in Table 2, and wherein detection method is according to GB/T
17657-2013 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " is carried out.
Table 2, the embodiment 5 Lauxite precipitation improvement proportioning of amino resin adhesive and testing result and comparative example 1
Testing result
Embodiment 6
Lauxite precipitation embodiment 3 obtained is separately added into commercially available E2 grade urea-formaldehyde resin adhesive, common
In melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde ternary polymerization adhesive, add
Before Lauxite precipitation, urea-formaldehyde resin adhesive and urea-melamine-formaldehyde ternary polymerization adhesive are used
20% formic acid adjusts pH value=4.5.Plywood is 5 layers of poplar assembly, resin added 240g/m2(two-sided applying glue),
Hot pressing temperature 115 DEG C, hot pressing time 1min/mm, hot pressing unit pressure 1MPa;Particieboard is poplar plane
Flower, designs density 0.65g/cm3, thickness 8mm, resin added 110kg/m3, hot pressing temperature 185 DEG C,
Hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa;Fibre board for aspen fibers by using silicon, design density
0.9g/cm3, thickness 9mm, resin added 120kg/m3, hot pressing temperature 200 DEG C, hot pressing time
1min/mm, hot pressing unit pressure 4MPa.
The Lauxite precipitation improvement proportioning of amino resin adhesive and result and without Lauxite precipitation
Amine resin wood-based plate quality index Comparative result is shown in Table 3, and wherein detection method is according to GB/T
17657-2013 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " is carried out.
Table 3, the embodiment 6 Lauxite precipitation improvement proportioning of amino resin adhesive and testing result and comparative example 1
Testing result
From the data of table 1-table 3 clearly it can be seen that amino resin adhesive add Lauxite precipitation after
Wood-based plate bonding strength can be significantly improved, reduce burst size of methanal.