CN101481593B - Preparation of urea-melamine-formaldehyde resin adhesive for E0-grade floor - Google Patents
Preparation of urea-melamine-formaldehyde resin adhesive for E0-grade floor Download PDFInfo
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- CN101481593B CN101481593B CN200910028357XA CN200910028357A CN101481593B CN 101481593 B CN101481593 B CN 101481593B CN 200910028357X A CN200910028357X A CN 200910028357XA CN 200910028357 A CN200910028357 A CN 200910028357A CN 101481593 B CN101481593 B CN 101481593B
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Abstract
The invention discloses a method for preparing a urea-melamine-formaldehyde resin adhesive for an E0-level floor. In the first step, formaldehyde solution, melamine and urea are mixed, the pH value of the mixture is regulated, the temperature is raised to 80-95 DEG C, and the reaction lasts 40-60 minutes, wherein, the mol ratio between formaldehyde and the total amount of the urea and the melamine is 2.05-2.12 : 1; in the second step, the pH value is regulated to be 5.0-6.0, and the reaction is underway till the turbidity point; in the third step, the pH value is regulated to be 6.0-6.9, the urea and the melamine are added, and the mol ratio between the formaldehyde and the total amount of the urea and the melamine which are added in the first step and the second step is 1.48-1.74 : 1, and the reaction lasts 30-70 min at a temperature of 90 DEG C; in the fourth step, the pH value is regulated to be 7.5-9.0, the melamine is added, and the reaction lasts 20-80 min at a temperature of 80-90 DEG C; and in the fifth step, the urea is added, the mol ratio between the formaldehyde and the total amount of all the urea and all the melamine is 1.02-1.30 : 1, and the material is cooled and discharged after the reaction is finished. A veneer formed by pressing the resin adhesive has good boiled-water resistance and low formaldehyde release, and the reaction is gentle and also easy to control.
Description
Technical field
The present invention relates to the preparation method of a kind of environment-friendly type floor, relate in particular to a kind of E with urea-formaldehyde resin adhesive
0The level floor is with the preparation method of low-cost cyanurotriamide modified urea resin glue.
Background technology
China is populous, forest reserves shortage, and area of woods has only 1/5 of world average level per capita, and along with the enforcement of China's wildwood protected project, and China's timber yield was by 3355.5 ten thousand m in 1997
3Adjust and reduce 1755.4 ten thousand m in 2000
3, and parties concerned's prediction, China's timber Minimum requirements amount was 200,000,000 m in 2000 to 2010
3, there is bigger contradiction in the timber supply and demand.The efficient main developing direction that becomes China's timber industry of utilizing of timber, according to estimates, 1m
3Wood-based plate can replace 3.1m
3The sheet material that log is processed, promptly tackiness agent is significant to improving timber utilization rate.
China's floor Total sales volume in 2007 is 3.51 hundred million m
3, wherein solid wooden floor board is 5,000 ten thousand m
3, solid wooden compound floor 7,000 ten thousand m
3, laminated flooring 2.2 hundred million m
3, bamboo floor 1,100 ten thousand m
3Main exit American-European countries, 1～September in 2007, exported wood floor 19.3 ten thousand t are worth 2.4 hundred million dollars.Urea-formaldehyde resin since its raw material be easy to get, cheap, ME is simple, advantage such as easy to use, is widely used in the manufacturing on consolidated floor, bamboo floor.But the UF Resin adhesive has poor water resistance and release formaldehyde two big shortcomings, and formaldehyde is harmful to HUMAN HEALTH, is considered to possible carcinogenic substance.The California, USA up-to-date regulation of making laws: 2009.1.1 day rises, and the wood veneer burst size of methanal need reach 0.08mg/Kg (macroclimate case method) could be sold, and 2010.1.1 day rises, and the wood veneer burst size of methanal need reach 0.05mg/Kg (macroclimate case method) and could sell.Present stage makes the floor of low formaldehyde release and adopts solid wooden floor board and expensive non-formaldehyde series tackiness agent mostly, and cost is high, and economic benefit is low.The wood-based plate of researching and developing low-cost low burst size of methanal and zero burst size of methanal is the tackling key problem object of all artificial board enterprises and related scientific research institutes, and this respect mainly concentrates in the modification of development that non-formaldehyde is tackiness agent and urea-formaldehyde resin.
It is raw material that non-formaldehyde series tackiness agent adopts isocyanic ester, starch etc. mostly, can discharge problem from solving artificial board formaldehyde in essence, obtains some progress.Like CN100999651, CN1982395, SY0800410102599.6 or the like, but because cost and technical elements, large-scale commercial prodn not as yet.
In recent years, the research of low artificial board formaldehyde burst size obtains remarkable progress.Urea-formaldehyde resin study on the modification to reducing burst size of methanal, raising bonding strength is comparatively active, like CN1834186, and CN1616510 etc.Existing E
0The level wood-based plate is with modified urea-formaldehyde resin glue prescription, preparation technology's report, like CN1632025, CN1570275, CN1526528, CN101244571.But this type of is limited to the manufacturing of three-ply-wood mostly, and need add properties-correcting agent etc. at glue, generally all need fall the aldehyde aftertreatment for multi-ply wood, and cost is higher, complicated operation.Do not make at present directly and anyly fall the aldehyde processing and just can reach E of muf resin glue compressed laminated wood
0The technology of level does not almost also have.
Summary of the invention
In order to solve the needs adding properties-correcting agent that prior art exists, the shortcoming that aldehyde is handled will be fallen after the making sheet, and the present invention provides a kind of E
0The level floor is with the preparation method of urea-melamine-formaldehyde resin adhesive, and technology is simple, need not to add other properties-correcting agent, and cost is lower, and aldehyde need not fall in the multi-ply wood of compacting to be handled.
Technical scheme of the present invention is: a kind of E
0The level floor is with the preparation method of urea-melamine-formaldehyde resin adhesive:
The first step: with the formaldehyde solution of 36.8%wt, account for formaldehyde solution quality 2.4～4.2% trimeric cyanamide, and first urea add reactor drum; Adjust pH to 8.0～10.0; Be warming up to 80 ℃～95 ℃; Reaction 40～60min, wherein, the mol ratio of formaldehyde/(urea+trimeric cyanamide) is 2.05～2.12: 1;
Second step: the pH value is transferred to 5.0～6.0, and 80～95 ℃ are reacted to cloud point;
The 3rd step: pH value is transferred to 6.0～6.9, add urea and with the trimeric cyanamide of the same quality of the first step, and the formaldehyde/mol ratio of (urea+trimeric cyanamide that the first step and the second step accumulative total add) is 1.48～1.74: 1,90 ℃ and reacts 30～70min;
The 4th step: the pH value is transferred to 7.5～9.0, add the trimeric cyanamide that accounts for formaldehyde quality 15～24%, 80-90 ℃ of reaction 20～80min;
The 5th step: add urea, and formaldehyde is 1.02～1.30: 1 with the urea that accumulative total adds with the mol ratio of trimeric cyanamide total amount, 20～80min, cooling discharging are reacted in continuation.
Wherein, it is sodium hydroxide or Pottasium Hydroxide that the adjust pH agents useful for same is transferred alkalescence, acid adjustment property be in ammonium chloride, formic acid, acetate, the hydrochloric acid any one.
Beneficial effect:
1. the present invention adopts alkali-acid-alkali traditional technology; Selected urea and trimeric cyanamide add in three batches; The urea gradation adds can play the effect that the molecular resin quality is regulated, and the urea that adds especially for the second time not only can be degraded and reset the macromole part in the molecule; But also can reduce the wherein content of ehter bond, reduce the burst size of formaldehyde.The pH value of strict control polycondensation phase with the method for two-stage polycondensation, can carry out polycondensation in order fast in building-up process.Adopt alkali stage to add first urea and trimeric cyanamide, the triazine ring of trimeric cyanamide has six active hydrogen atoms, can with the formaldehyde addition reaction, generate hexamethylolmelamine.Hexamethylolmelamine can polycondensation becomes with-CH
2-or-CH
2OHCH
2The melamine resin of-link also can become cyanurotriamide modified urea-formaldehyde resin with methylolurea or the urea-formaldehyde resin polycondensation that contains methylol.Multi-functional melamine molecule is introduced in the urea-formaldehyde resin of modification, has promoted urea-formaldehyde resin to form the crosslinking reaction of tridimensional network, has improved the water proof bonding strength of wood-based plate.Trimeric cyanamide has certain shock absorption, can suppress the reduction of pH value, prevents and reduced the hydrolysis rate of urea-formaldehyde resin to a certain extent, can improve the package stability of resin.The link melamine molecule-CH
2OCH
2-more stable, do not resemble that condensation between the methylolurea forms-CH
2OCH
2-chain is prone to decompose discharge formaldehyde, thereby adds the cyanurotriamide modified burst size of methanal that can reduce the urea-formaldehyde glue wood-based plate.
2. the patent publication No. of having applied for respect to us is CN101244571's " preparation method of E0 level plywood " patent; The present invention is conceived to prescription, the technology of glue; Through improvement and the optimization to glue prescription, technology, the wood veneer of compacting has resistance to boiling water and lower burst size of methanal preferably.As far as the floor, must have certain resistance to boiling water is not peel off after having certain bonding strength and oven dry behind 100 ℃ of poach 3h.Because this glue water tolerance, tack are good, initial reaction stage need not add Z 150PH, reduces cost.Acid adjustment, alkali agents useful for same are ammonium chloride, sodium hydroxide, and ammonium chloride can progressively discharge HCl after adding, and progressively reduces pH value in reaction, react gentle easy to control, and its price is lower, further reduces cost, and its comparative test result sees attached list 4.
3. the mol ratio of formaldehyde/urea is 1.3～1.5 among the present invention; Guaranteed the intensity of wood veneer behind the resin solidification; And added the trimeric cyanamide of certain mass and adopt in the promotion further of low temperature synthesis technique the abundant reaction of formaldehyde; So the free formaldehyde in institute's synthetic resins is very low, is low toxic and environment-friendly type urea-formaldehyde resin.
4. preparation technology of the present invention is simple, and reproducibility is good, and reacting balance is easy to control, and storage period is long.Promptly reached E in 7～10 days with placing behind institute's synthetic resin compressed laminated wood
0The level requirement need not passed through any aldehyde aftertreatment of falling, and is simple to operate.And Recipe (example 7, the example 8) trimeric cyanamide by the selected industrial scale pressing plate of example 1, routine 2 Recipes adds quality less than 14.0% of urea-melamine-formaldehyde resin total mass among the present invention, and cost is lower.
Embodiment:
A kind of E
0The level floor is with the preparation method of urea-melamine-formaldehyde resin adhesive:
The first step: with the formaldehyde solution of 36.8%wt, account for formaldehyde solution quality 2.4～4.2% trimeric cyanamide, and first urea add reactor drum; Adjust pH to 8.0～10.0; Be warming up to 80 ℃～95 ℃; Reaction 40～60min, wherein, the mol ratio of formaldehyde/(urea+trimeric cyanamide) is 2.05～2.12: 1;
Second step: the pH value is transferred to 5.0～6.0, and 80～95 ℃ are reacted to cloud point;
The 3rd step: pH value is transferred to 6.0～6.9, add urea and with the trimeric cyanamide of the same quality of the first step, and the formaldehyde/mol ratio of (urea+trimeric cyanamide that the first step and the second step accumulative total add) is 1.48～1.74: 1,90 ℃ and reacts 30～70min;
The 4th step: the pH value is transferred to 7.5～9.0, add the trimeric cyanamide that accounts for formaldehyde quality 15～24%, 80-90 ℃ of reaction 20～80min;
The 5th step: add urea, and formaldehyde is 1.02～1.30: 1 with the urea that accumulative total adds with the mol ratio of trimeric cyanamide total amount, 20～80min, cooling discharging are reacted in continuation.
Wherein, it is sodium hydroxide or Pottasium Hydroxide that the adjust pH agents useful for same is transferred alkalescence, acid adjustment property be in ammonium chloride, formic acid, acetate, the hydrochloric acid any one.
Accent alkali reagent in following examples is the 15wt%NaOH aqueous solution, and acid adjustment reagent is the NH of 20wt%
4The Cl aqueous solution.
Instance 1
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 7.5g, reach first urea 84g adding reactor drum, adjust pH to 7.5 is warming up to 80 ℃～90 ℃, reaction 40min.
Second step: the pH value is transferred to 5.0,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.5, add second crowd of trimeric cyanamide 7.5g and second crowd of urea 29g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 7.5, add the 3rd crowd of trimeric cyanamide 45g, 80 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 29g, 50 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Press the poplar three-ply-wood for solidifying agent, test result sees attached list 2.
Instance 2
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 7.5g, reach first urea 84g adding reactor drum, adjust pH to 8.0 is warming up to 85 ℃, reaction 45min.
Second step: the pH value is transferred to 5.5,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.5, add second crowd of trimeric cyanamide 7.5g and second crowd of urea 24g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 8.0, add the 3rd crowd of trimeric cyanamide 45g, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 24g, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Press the poplar three-ply-wood for solidifying agent, test result sees attached list 2.
Instance 3
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 9g, reach first urea 84g adding reactor drum, adjust pH to 9.0 is warming up to 90 ℃, reaction 50min.
Second step: the pH value is transferred to 5.8,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 9g and second crowd of urea 29g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 9.0, add the 3rd crowd of trimeric cyanamide 52g, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 29g, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Press the poplar three-ply-wood for solidifying agent, test result sees attached list 2.
Instance 4
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 9g, reach first urea 84g adding reactor drum, adjust pH to 9.0 is warming up to 90 ℃, reaction 50min.
Second step: the pH value is transferred to 6.0,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 9g and second crowd of urea 19g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 9.0, add the 3rd crowd of trimeric cyanamide 52g, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 19g, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Press the poplar three-ply-wood for solidifying agent, test result sees attached list 2.
Instance 5
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 10.5g, reach first urea 84g adding reactor drum, adjust pH to 8.5 is warming up to 80 ℃～90 ℃, reaction 60min.
Second step: the pH value is transferred to 5.8,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 10.5g and second crowd of urea 29g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 8.0, add the 3rd crowd of trimeric cyanamide 59g, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 29g, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Be solidifying agent compacting poplar three-ply-wood, test result sees attached list 2.
Instance 6
The first step: in the 500ml four-hole boiling flask, add 250g formaldehyde solution, first trimeric cyanamide 10.5g, reach first urea 84g adding reactor drum, adjust pH to 8.5 is warming up to 90 ℃, reaction 50min.
Second step: the pH value is transferred to 5.6,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 10.5g and second crowd of urea 15.5g, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 8.0, add the 3rd crowd of trimeric cyanamide 59g, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 15.5g, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Be solidifying agent compacting poplar three-ply-wood, test result sees attached list 2.
Instance 7
The first step: in the 2t reaction kettle, add 1164kg formaldehyde solution, first trimeric cyanamide 35kg, reach first urea 391kg adding reactor drum, adjust pH to 8.6 is warming up to 80 ℃～90 ℃, reaction 40～50min.
Second step: the pH value is transferred to 5.6,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 35kg and second crowd of urea 111kg, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 8.5, add the 3rd crowd of trimeric cyanamide 210kg, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 112kg, 55 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Press Eucalyptus three, five, seven, nine plywood for solidifying agent, test result sees attached list 3.
Instance 8
The first step: in the 2t reaction kettle, add 1400g formaldehyde solution, first trimeric cyanamide 42kg, reach first urea 470kg adding reactor drum, adjust pH to 8.5 is warming up to 90 ℃, reaction 50min.
Second step: the pH value is transferred to 5.4,90 ℃ of reactions to required viscosity.
The 3rd step: the pH value is transferred to 6.9, add second crowd of trimeric cyanamide 42kg and second crowd of urea 135kg, 90 ℃ of reaction 50min.
The 4th step: the pH value is transferred to 8.5, add the 3rd crowd of trimeric cyanamide 252kg, 90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 134kg, 60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1.And adopt 1% NH
4Cl and 0.5% H
3PO
4Be solidifying agent compacting linden-poplar-linden three, five-ply board, test result sees attached list 3.
Instance 9
The first step: in the 3t reaction kettle, add 1800kg formaldehyde solution, 10kg Z 150PH, first trimeric cyanamide 45kg, reach first urea 600kg adding reactor drum; With trolamine adjust pH to 7.5～8.0; Be warming up to 80 ℃～90 ℃, reaction 40～50min.
Second step: the formic acid with 50% transfers to 5.0～5.4 with the pH value, 90 ℃ of reaction to required viscosity.
The 3rd step: with trolamine the pH value is transferred to 6.5～6.9, add second crowd of trimeric cyanamide 45kg and second crowd of urea 240kg, 90 ℃ of reaction 50min.
The 4th step: with trolamine the pH value is transferred to 7.5～8.0, add the 3rd crowd of trimeric cyanamide 185kg, 80-90 ℃ of reaction 40min.
The 5th step: be cooled to 70 ℃, add the 3rd crowd of urea 336kg, 50～60 ℃ are continued reaction 30min, cooling discharging.Test its performance respectively, the result lists in subordinate list 1, and adopts 1% NH
4Cl and 0.5% H
3PO
4Be solidifying agent compacting poplar three-ply-wood, test result sees attached list 4.
Subordinate list 1:E
0The urea-melamine-formaldehyde resin adhesive technical indicator is used on the level floor
| The formaldehyde/urea mol ratio | Solid content (%) | Viscosity (25 ℃) (mPa.s) | Free formaldehyde (%) | Set time (S) | Storage period (d) | |
| Instance 1 | 1.3 | 57.8 | 78 | 0.09 | 146 | ＞15 |
| Instance 2 | 1.4 | 56.7 | 60 | 0.10 | 150 | ＞15 |
| Instance 3 | 1.3 | 58.9 | 82 | 0.08 | 170 | ＞15 |
| Instance 4 | 1.5 | 57.0 | 51 | 0.07 | 110 | ＞15 |
| Instance 5 | 1.3 | 54.6 | 38 | 0.10 | 190 | ＞15 |
| Instance 6 | 1.6 | 54.2 | 39 | 0.08 | 108 | ＞15 |
| Instance 7 | 1.4 | 51.5 | 24 | 0.13 | 104 | ＞15 |
| Instance 8 | 1.4 | 51.3 | 52 | 0.12 | 110 | ＞15 |
| Instance 9 | 1.2 | 55.8 | 38 | 0.08 | 196 | ＞30 |
In the subordinate list 1, the free formaldehyde of the urea-melamine-formaldehyde resin adhesive of preparation is all less than 0.15%, and viscosity is during less than 100mPa.s, and storage period is all more than 15 days.
Subordinate list 2:E
0The level floor is with urea-melamine-formaldehyde resin adhesive pressing plate test result
Annotate: Strength of Plywood is 14 test specimen detected results in the subordinate list 2, and molecule is average bonding strength, and denominator is minimum intensity～maximum intensity.
In the subordinate list 2, with the poplar three-ply-wood that the urea-melamine-formaldehyde resin adhesive of preparation is suppressed, burst size of methanal≤0.5mg/L reaches E
0Level; Bonding strength reaches the requirement of national II class plate, still has certain bonding strength behind 100 ℃ of poach 3h, has certain resistance to boiling water.The formaldehyde/urea mol ratio of instance 1,3,5 is lower, and its burst size of methanal and bonding strength are lower, and the formaldehyde/urea mol ratio is high more, and resistance to boiling water is good more.
Subordinate list 3:E
0The level floor produces the pressing plate test result with urea-melamine-formaldehyde resin adhesive
In the subordinate list 3, three, five, seven, the nine plywood burst size of methanal of producing compacting reach E
0Level, bonding strength meets the requirement of national II class plate, and the number of plies of wood veneer increases, and its burst size of methanal slightly changes, but changes little.
Subordinate list 4:E
0Level floor and E
0Level plywood (CN101244571) comparative test result
Subordinate list 4, owing in the present invention glue prescription, technology have been carried out adjustment largely, bonding strength and resistance to boiling water all are better than the wood veneer of urea-melamine-formaldehyde resin adhesive compacting among the CN101244571.
The detection of above-mentioned urea-melamine-formaldehyde resin: 3.5 regulations that solids content is pressed GB/T14074-2006 detect; 3.3 regulations that viscosity is pressed GB/T14074-2006 detect; 3.7 regulations of pressing GB/T14074-2006 set time detect; Free formaldehyde is pressed 3.16 of GB/T14074-2006 and is detected.The solids content unification refers to the solids content of institute's glue, and free formaldehyde content is the massfraction of the contained monomer formaldehyde in the inside of whole glue.
The detection of wood veneer: the wood veneer room temperature of compacting is placed after 5～7 days and is detected.Bonding strength is pressed 4.15 regulation detections among the GB/T17657-1999; Burst size of methanal detects by 4.12 moisture eliminator methods among the GB/T17657-1999.
Claims (1)
1. E
0The level floor is characterized in that with the preparation method of urea-melamine-formaldehyde resin adhesive:
The first step: with the formaldehyde solution of 36.8%wt, account for formaldehyde solution quality 2.4～4.2% trimeric cyanamide, and first urea add reactor drum; Adjust pH to 8.0～10.0; Be warming up to 80 ℃～95 ℃; Reaction 40～60min, wherein, the mol ratio of formaldehyde/(urea+trimeric cyanamide) is 2.05～2.12: 1;
Second step: the pH value is transferred to 5.0～6.0, and 80～95 ℃ are reacted to cloud point;
The 3rd step: pH value is transferred to 6.0～6.9, add urea and with the trimeric cyanamide of the same quality of the first step, and the formaldehyde/mol ratio of (urea+trimeric cyanamide that the first step and the second step accumulative total add) is 1.48～1.74: 1,90 ℃ and reacts 30～70min;
The 4th step: the pH value is transferred to 7.5～9.0, add the trimeric cyanamide that accounts for formaldehyde quality 15～24%, 80-90 ℃ of reaction 20～80min;
The 5th step: add urea, and formaldehyde is 1.02～1.30: 1 with the urea that accumulative total adds with the mol ratio of trimeric cyanamide total amount, 20～80min, cooling discharging are reacted in continuation;
It is sodium hydroxide or Pottasium Hydroxide that the adjust pH agents useful for same is transferred alkalescence, acid adjustment property be in ammonium chloride, formic acid, acetate, the hydrochloric acid any one.
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|---|---|---|---|
| CN200910028357XA CN101481593B (en) | 2009-01-14 | 2009-01-14 | Preparation of urea-melamine-formaldehyde resin adhesive for E0-grade floor |
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|---|---|---|---|
| CN200910028357XA CN101481593B (en) | 2009-01-14 | 2009-01-14 | Preparation of urea-melamine-formaldehyde resin adhesive for E0-grade floor |
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| CN101481593B true CN101481593B (en) | 2012-02-01 |
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| CN105348464B (en) * | 2015-12-20 | 2017-10-31 | 江西绿洲环保新材料股份有限公司 | The preparation method of environment-friendly modified urea-formaldehyde resin adhesive |
| CN107383299A (en) * | 2016-05-16 | 2017-11-24 | 华南理工大学 | One kind is used to manufacture ecological floor modified urea-formaldehyde resin and preparation method thereof |
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|---|---|---|---|---|
| CN101244571A (en) * | 2008-03-21 | 2008-08-20 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing E0 level wood veneer |
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2009
- 2009-01-14 CN CN200910028357XA patent/CN101481593B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244571A (en) * | 2008-03-21 | 2008-08-20 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing E0 level wood veneer |
Non-Patent Citations (3)
| Title |
|---|
| 王春鹏等."E0级胶合板用低成本UMF树脂胶的研制".《林产工业》.2007,(第6期),46-50. |
| 王春鹏等."低毒胶合板用脲醛树脂胶粘剂的研究".《林产工业》.2000,第27卷(第6期),21-23，28. |
| 王春鹏等."低毒胶合板用脲醛树脂胶粘剂的研究".《林产工业》.2000,第27卷(第6期),21-23,28. * |
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| CN101481593A (en) | 2009-07-15 |
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