Background technology
Amine resin tackiness agent is the tackiness agent of timber industry consumption maximum, accounts for the more than 90% of Wood-based Panel Production glue consumption, because its cost advantage can't be replaced by other tackiness agent so far.The amino resin adhesive that prior art is produced, the greatest problem existing in use is that especially hot water resistance can be not strong for water tolerance, due to the deficiency in formulating of recipe, the burst size of methanal that glueds joint goods is larger, is perplexing the production of timber industry and wood-based plate final user's use always in addition.
With gradation, add urea, the synthetic urea-formaldehyde resin adhesive of method that reduces whole mol ratio is one of effective ways that solve burst size of methanal; With urea-melamine-formaldehyde terpolymer mode synthetic amino resin tackiness agent, it is the another kind of method that effectively reduces burst size of methanal.Above method also can cause disadvantageous effect to amino resin adhesive simultaneously, and as stability in storage declines, bonding strength declines, water tolerance reduction etc.With nanometer particle-modified amine resin tackiness agent, be little based on nano particle diameter, specific surface area is large, surface can be high, a large amount of unsaturated residual bonds are contained on surface, reactive behavior is high, and between amine resin tackiness agent, there is even response capacity of very strong interaction, not only can reduce the burst size of methanal of amine resin tackiness agent, can also improve bonding strength.Chinese patent literature CN101818036A discloses a kind of method of silicate nano-clay modified urea-formaldehyde resin adhesive; Chinese patent literature CN102276734A discloses the method for the cellulose modified urea-formaldehyde resin adhesive of a kind of nanocrystal; Chinese patent literature CN101696348B discloses the method for the nano-titanium dioxide modified urea-formaldehyde resin adhesive of a kind of use; Chinese patent literature CN101747853B discloses a kind of method of organic amine composite Nano zirconium phosphate modified urea-formaldehyde resin adhesive; Chinese patent literature CN101880437A discloses a kind of method that adopts the modified urea-formaldehyde resin adhesives such as nano titanium oxide, nano silicon, nano-calcium carbonate; Chinese patent literature CN103275660A discloses a kind of method that adopts carbon nano-tube modification urea-formaldehyde resin adhesive.But above method all adopts inorganic nano material, and the preparation method of relevant nano material is comparatively complicated, and price is comparatively expensive, causes modification high cost, is not suitable with the present situation of wood-based panel industry low cost fabrication industry.
Chinese patent literature CN102898664A discloses a kind of preparation method of urea-formaldehyde resin microballoon, (1) prepare urea-formaldehyde resin prepolymer: in reactor, add water, dispersion agent, stirring and dissolving is even, then adds urea, formaldehyde, adopts alkaline matter to adjust pH value to alkalescence; Then be heated to 40~90 ℃, polyreaction 0.5~5 hour, obtains urea-formaldehyde resin prepolymer; (2) prepare resin solidification liquid: in another reactor, add water, solidifying agent, stirring and dissolving is even, be warming up to 40~70 ℃, obtain the resin solidification liquid that pH value is 0.1-3.0; (3) urea-formaldehyde resin prepolymer temperature is adjusted to 40~70 ℃, then adopts dropping equipment evenly to splash in resin solidification liquid and be cured reaction; After reaction finishes, then neutralize, filter, obtain urea-formaldehyde resin microballoon; Formaldehyde in described step (1) is that solid formaldehyde is or/and liquid formaldehyde solution; The mol ratio of urea and formaldehyde is 1-2:1.Obtain at the urea-formaldehyde resin microballoon aspect structure and size with very high homogeneity.
Chinese patent literature CN102993393A discloses a kind of method of urea-formaldehyde resin microballoon of synthetic uniform grading distribution, by adding tensio-active agent, urea and formaldehyde to prepare after urea-formaldehyde resin precipitation in distilled water, suction filtration washing obtain urea-formaldehyde resin microballoon, the mol ratio of formaldehyde and urea is 2:1, the sedimentary microscopic appearance of gained is spherical, can be used for chromatograph packing material, support of the catalyst, tackiness agent, super capacitor material and environmental pollution treatment aspect.
Summary of the invention
The synthetic method that the object of this invention is to provide the urea-formaldehyde resin precipitation that a kind of making method is simplified, cost is low.
For reaching goal of the invention, the technical solution used in the present invention is: a kind of synthetic method of urea-formaldehyde resin precipitation, the steps include:
(6) formaldehyde solution is transferred to pH value 1-5 with strong acid; Concentration of formaldehyde 35-38%;
(1) formaldehyde/urea=0.5-1 in molar ratio, is added into urea in formaldehyde solution;
(2) under 30-90 ℃, agitation condition, react, when occurring that white cloud is muddy, continue stirring reaction 1-3h, be then down to room temperature and obtain urea-formaldehyde resin precipitation solution;
(3) by the urea-formaldehyde resin precipitation solution obtaining through the ultrasonic concussion processing that homogenizes, the treatment time is 15-120min, ultrasonic power 1000-1500W;
(4) urea-formaldehyde resin precipitation solution suction filtration is obtained to urea-formaldehyde resin and precipitate and be washed to neutrality, under 30-70 ℃ of condition, be dried to constant weight.
Preferably, described strong acid is selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid or di-carboxylic acid.
The present invention reacts with urea formaldehyde under strong acid, low mol ratio condition, do not need to use tensio-active agent, do not need to add solidifying agent or other materials yet, after supersound process, the urea-formaldehyde resin obtaining is precipitated as micron, Nano grade, and its surface topography presents flakey, merges ball, spherical, suede ball, suede merge ball and lamella blending in of fibers structure etc.
The invention also discloses urea-formaldehyde resin precipitation that aforesaid method obtains as the application of amine resin tackiness agent modifying agent.
The method of this application is: amine resin precipitation is added in amine resin tackiness agent by a certain percentage, stir, the mass ratio of interpolation is amine resin tackiness agent: urea-formaldehyde resin precipitation=100:5-30.
Preferably, described amine resin tackiness agent is urea-formaldehyde resin adhesive, melamine formaldehyde resin adhesives or urea-melamine-formaldehyde terpolymer resin tackiness agent.
Preferably, first the pH value of the urea-formaldehyde resin adhesive in amine resin tackiness agent or urea-melamine-formaldehyde terpolymer resin tackiness agent is adjusted to 4.5 before adding amine resin precipitation, the pH value of melamine formaldehyde resin adhesives does not adjust.
The urea-formaldehyde resin precipitation that the synthetic method of urea-formaldehyde resin precipitation of the present invention obtains is added amine resin tackiness agent to, greatly improve bonding strength, reduce burst size of methanal, and do not change the operation condition of current wood-based panel industry amine resin tackiness agent, add after urea-formaldehyde resin precipitation, amine resin tackiness agent, still with existing resin application methods and resin added applying glue, is produced wood-based plate with existing Wood-based Panel Production method.
Embodiment
Embodiment 1
(1) with the formaldehyde solution pH that hydrochloric acid is 35% by concentration, be adjusted to 2;
(2) formaldehyde/urea=0.6 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) under 45 ℃, agitation condition, react, when occurring that white cloud is muddy, continue stirring reaction 2h, be then down to room temperature and obtain urea-formaldehyde resin precipitation solution;
(4) by the urea-formaldehyde resin precipitation solution obtaining through the ultrasonic concussion processing that homogenizes, the treatment time is 120min; Ultrasonic power 1000W;
(5) urea-formaldehyde resin precipitation solution suction filtration is obtained to urea-formaldehyde resin and precipitate and be washed to neutrality, under 40 ℃ of conditions, be dried to constant weight.
The particle size range of the urea-formaldehyde resin precipitation obtaining is 500nm-1 μ m, and its configuration of surface is shown in Fig. 1.
Embodiment 2
(1) with the formaldehyde solution pH that sulfuric acid is 38% by concentration, be adjusted to 1;
(2) formaldehyde/urea=0.5 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) under 30 ℃, agitation condition, react, when occurring that white cloud is muddy, continue stirring reaction 1h, be then down to room temperature and obtain urea-formaldehyde resin precipitation solution;
(4) by the urea-formaldehyde resin precipitation solution obtaining through the ultrasonic concussion processing that homogenizes, the treatment time is 20min; Ultrasonic power 1200W;
(5) urea-formaldehyde resin precipitation solution suction filtration is obtained to urea-formaldehyde resin and precipitate and be washed to neutrality, under 30 ℃ of conditions, be dried to constant weight.
The particle size range of the urea-formaldehyde resin precipitation obtaining is 800nm-1 μ m, and its configuration of surface is shown in Fig. 2.
Embodiment 3
(1) with the formaldehyde solution pH that hexanodioic acid is 36% by concentration, be adjusted to 5;
(2) formaldehyde/urea=1 in molar ratio, is added into industrial urea in industrial formaldehyde solution;
(3) under 90 ℃, agitation condition, react, when occurring that white cloud is muddy, continue stirring reaction 3h, be then down to room temperature and obtain urea-formaldehyde resin precipitation solution;
(4) by the urea-formaldehyde resin precipitation solution obtaining through the ultrasonic concussion processing that homogenizes, the treatment time is 15min, ultrasonic power 1500W;
(5) urea-formaldehyde resin precipitation solution suction filtration is obtained to urea-formaldehyde resin and precipitate and be washed to neutrality, under 70 ℃ of conditions, be dried to constant weight.
The particle size range of the urea-formaldehyde resin precipitation obtaining is 1-10 μ m, and its configuration of surface is shown in Fig. 3.
Comparative example 1
Commercially available E2 grade urea-formaldehyde resin tackiness agent, common melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde terpolymer tackiness agent do not add urea-formaldehyde resin precipitation, by urea-formaldehyde resin adhesive and urea-melamine-formaldehyde terpolymer tackiness agent with 20% formic acid adjust pH=4.5.Glued board is 5 layers of poplar assembly, resin added 240g/m
2(two-sided applying glue), 115 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 1MPa; Shaving board is Aspen wood shavings, design density 0.65g/cm
3, thickness 8mm, resin added 110kg/m
3, 185 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa; Fiberboard be aspen fibers by using silicon, design density 0.9g/cm
3, thickness 9mm, resin added 120kg/m
3, 200 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 4MPa.
Embodiment 4
The urea-formaldehyde resin precipitation that embodiment 1 is obtained adds respectively in commercially available E2 grade urea-formaldehyde resin tackiness agent, common melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde terpolymer tackiness agent, adds before urea-formaldehyde resin precipitation urea-formaldehyde resin adhesive and urea-melamine-formaldehyde terpolymer tackiness agent with 20% formic acid adjust pH=4.5.Glued board is 5 layers of poplar assembly, resin added 240g/m
2(two-sided applying glue), 115 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 1MPa; Shaving board is Aspen wood shavings, design density 0.65g/cm
3, thickness 8mm, resin added 110kg/m
3, 185 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa; Fiberboard be aspen fibers by using silicon, design density 0.9g/cm
3, thickness 9mm, resin added 120kg/m
3, 200 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 4MPa.
The wood-based plate quality index result of urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the amine resin wood-based plate quality index result contrast of not adding urea-formaldehyde resin precipitation are in Table 1, and wherein detection method is carried out according to GB/T17657-2013 < < Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels > >.
The proportioning of table 1, embodiment 4 urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the detected result of detected result and comparative example 1
Embodiment 5
The urea-formaldehyde resin precipitation that embodiment 2 is obtained adds respectively in commercially available E2 grade urea-formaldehyde resin tackiness agent, common melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde terpolymer tackiness agent, adds before urea-formaldehyde resin precipitation urea-formaldehyde resin adhesive and urea-melamine-formaldehyde terpolymer tackiness agent with 20% formic acid adjust pH=4.5.Glued board is 5 layers of poplar assembly, resin added 240g/m
2(two-sided applying glue), 115 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 1MPa; Shaving board is Aspen wood shavings, design density 0.65g/cm
3, thickness 8mm, resin added 110kg/m
3, 185 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa; Fiberboard be aspen fibers by using silicon, design density 0.9g/cm3, thickness 9mm, resin added 120kg/m
3, 200 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 4MPa.
The wood-based plate quality index result of urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the amine resin wood-based plate quality index result contrast of not adding urea-formaldehyde resin precipitation are in Table 2, and wherein detection method is carried out according to GB/T17657-2013 < < Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels > >.
The proportioning of table 2, embodiment 5 urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the detected result of detected result and comparative example 1
Embodiment 6
The urea-formaldehyde resin precipitation that embodiment 3 is obtained adds respectively in commercially available E2 grade urea-formaldehyde resin tackiness agent, common melamine formaldehyde resin adhesives and E2 level urea-melamine-formaldehyde terpolymer tackiness agent, adds before urea-formaldehyde resin precipitation urea-formaldehyde resin adhesive and urea-melamine-formaldehyde terpolymer tackiness agent with 20% formic acid adjust pH=4.5.Glued board is 5 layers of poplar assembly, resin added 240g/m
2(two-sided applying glue), 115 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 1MPa; Shaving board is Aspen wood shavings, design density 0.65g/cm
3, thickness 8mm, resin added 110kg/m
3, 185 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 2.5MPa; Fiberboard be aspen fibers by using silicon, design density 0.9g/cm
3, thickness 9mm, resin added 120kg/m
3, 200 ℃ of hot pressing temperatures, hot pressing time 1min/mm, hot pressing unit pressure 4MPa.
Proportioning and the result of urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the amine resin wood-based plate quality index result contrast of not adding urea-formaldehyde resin precipitation are in Table 3, and wherein detection method is carried out according to GB/T17657-2013 < < Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels > >.
The proportioning of table 3, embodiment 6 urea-formaldehyde resin precipitation improvement amine resin tackiness agent and the detected result of detected result and comparative example 1
From the data of table 1-table 3, clearly can find out, in amine resin tackiness agent, add after urea-formaldehyde resin precipitates and can obviously improve wood-based plate bonding strength, reduce burst size of methanal.