CN105504193B - Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive and preparation method thereof - Google Patents
Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive and preparation method thereof Download PDFInfo
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- CN105504193B CN105504193B CN201610073566.6A CN201610073566A CN105504193B CN 105504193 B CN105504193 B CN 105504193B CN 201610073566 A CN201610073566 A CN 201610073566A CN 105504193 B CN105504193 B CN 105504193B
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
Abstract
The present invention discloses a kind of Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive, includes the raw material of following parts by weight：Mass percent concentration is 36.8% 37.2% 40 60 parts of formalin, 30 45 parts of urea, 5 25 parts of melamine, 1 10 parts of modifying agent；It is E that the present invention, which can produce environmental protection grade,0The moistureproof adhesive of level, technique is flexibly simple, production efficiency is high, and resin dispersion can be also effectively improved to fiberboard environmental protection and moistureproof demand, preparation method of the invention by meeting people, promoted cementitiousness, reduced free formaldehyde, lift adhesive water resistance.
Description
Technical field
The present invention relates to a kind of Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive and preparation method thereof.
Background technology
Its good processing characteristics due to medium and high density fibre panel, it has been widely used in being applied to medium-to-high grade furniture system
Make, interior decoration, loudspeaker casing, musical instrument, the industry such as car and boat interior decoration.With the improvement of people's living standards, fiberboard is removed
Have outside good processing characteristics, it is also necessary to more environmentally friendly and with the functions such as moistureproof and waterproof, particularly environmental protection and moisture barrier properties, row
At first, second of the other functional requirements of fiberboard.It is fine because fiberboard has used Lauxite stick in process of production
The release that will unavoidably have free formaldehyde in dimension plate, formaldehyde are unfavorable to health it is verified that with certain toxicity；
The humidity resistance of fiberboard can then open application field of the fiberboard among wet environment, widen fiberboard accommodation.
So developing a kind of environmental protection grade reaches E0Level, while but also with the urea-formaldehyde resin adhesive of humidity resistance, there is great warp
Benefit of helping and social benefit.
The content of the invention
The technical problems to be solved by the invention are the shortcomings that overcoming above prior art：A kind of environmental protection grade is provided to reach
To E0Level, while cyanurotriamide modified urea resin adhesive but also with humidity resistance and preparation method thereof.
The technical solution of the present invention is as follows：A kind of Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive, including
The raw material of following parts by weight：Mass percent concentration be 36.8%-37.2% formalin 40-60 parts, urea 30-45 parts,
Melamine 5-25 parts, modifying agent 1-10 parts.
Described modifying agent is the one or more in triethanolamine, diethylene glycol, oxidized starch, hydrogen peroxide, phenol.
Preferably, described modifying agent is triethanolamine, hydrogen peroxide using weight ratio as 2:The mixture of 1 mixing.
Preferably, described modifying agent is triethanolamine, oxidized starch, hydrogen peroxide using weight ratio as 5:8:2 mixing
Mixture.
Preferably, described modifying agent is diethylene glycol, oxidized starch, hydrogen peroxide, phenol using weight ratio as 5:6:
2:The mixture of 1 mixing.
Preferably, described modifying agent is triethanolamine, diethylene glycol, hydrogen peroxide using weight ratio as 2:2:1 mixing
Mixture.
A kind of preparation method of described Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive, comprises the following steps：
1）Weighed by proportioning and formalin is put into reactor after each raw material, after stirring, add modifying agent gross weight
10%-30% first modifying agent, it is 9.0-9.5 to adjust reacting solution pH value using sodium hydrate aqueous solution；
2）Reaction solution is heated to 45 DEG C, continues to be heated to 60-65 DEG C after adding melamine, insulation
10-15 minutes；
3）First urea is added, it is F/U to make the mol ratio of formaldehyde and urea1=1.85-2.05, is warming up to 85-92 DEG C,
It is incubated 25-35 minutes；
4）It is 85-88 DEG C to adjust reaction solution temperature, and it is 4.8-6.8 to adjust pH value with aqueous formic acid, in 85-92 DEG C of temperature
Degree is lower to carry out polycondensation reaction；
5）It is whole for first reaction when viscosity is the 16-18 seconds using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution
Point；
6）After reaching first reaction end, it is 5.8-7.5 to adjust reacting solution pH value with sodium hydrate aqueous solution, is added
Second batch urea, it is F/U to make the mol ratio of formaldehyde and urea2=1.15-1.25；
7）Second batch urea is added after 5 minutes, using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, when viscosity is 18-
It is second reaction end at 20 seconds；
8）Remaining modifying agent is added, it is 7.6-8.8 to adjust reacting solution pH value with sodium hydrate aqueous solution, is incubated 10-15
Minute；
9）The 3rd batch of urea is added, it is F/U to make the mol ratio of formaldehyde and urea3=0.88-0.97, it is incubated 10-15 minutes
Afterwards, cool；
10）38-43 DEG C is cooled to, pH value is adjusted to 7.5-8.8, discharging with sodium hydrate aqueous solution.
The beneficial effects of the invention are as follows：The present invention by the comprehensive functions of a variety of modifying agent and specific preparation method
With reference to the bonding property for effectively increasing Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive, make the reduction of its cost；Can be with
Production environmental protection grade is E0The moistureproof adhesive of level, technique is flexibly simple, production efficiency is high, meets people to fiberboard ring
Protect again moistureproof demand.The preparation method of the present invention can also be effectively improved resin dispersion, promote cementitiousness, reduce free first
Aldehyde, lift adhesive water resistance.
Embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact
Apply example.
Embodiment 1
The formalin 550kg that mass percent concentration is 36.8%-37.2% is put into reactor, after stirring, risen
Temperature heating, adds first modifying agent（Triethanolamine, hydrogen peroxide are using weight ratio as 2:The mixture of 1 mixing）3kg, use
25% sodium hydrate aqueous solution adjustment reacting solution pH value is 9.0-9.5.When being warming up to 45 DEG C, stop heating, add melamine
48kg, continue heating heating after addition；It is heated to stopping heating at 60 DEG C, is incubated 10 minutes.The 1st is added at 60-65 DEG C
Urea 168kg is criticized, it is F/U to make the mol ratio of formaldehyde and urea1=2.05,92 DEG C are warming up to, is incubated 30 minutes.85 DEG C are cooled to,
It is 5.0-5.8 with 25% aqueous formic acid regulation pH value, polycondensation reaction is carried out at a temperature of 85 DEG C.Examined using -4 viscosity agar diffusion methods are applied
The terminal of reaction solution is surveyed, is first reaction end when viscosity is the 16-18 seconds.After reaching first reaction end, with 25%
Sodium hydrate aqueous solution adjustment reacting solution pH value is 5.8-6.5, adds the 2nd crowd of urea 138kg, makes mole of formaldehyde and urea
Than for F/U2=1.22.The 2nd batch of urea is added after 5 minutes, using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, when viscosity is
It is second reaction end during the 18-20 seconds.Add remaining modifying agent（Triethanolamine, hydrogen peroxide are using weight ratio as 2:1 mixing
Mixture）9kg, it is 7.6-8.2 to adjust reacting solution pH value with sodium hydrate aqueous solution, is incubated 10 minutes.Add the 3rd batch of urine
Plain 90kg, it is F/U to make the mol ratio of formaldehyde and urea3=0.96, after being incubated 10 minutes, cool.38-43 DEG C is cooled to, hydrogen
Aqueous solution of sodium oxide adjusts pH value 7.5-8.3, discharging.
Embodiment 2
The formalin 680kg that mass percent concentration is 36.8%-37.2% is put into reactor, after stirring, risen
Temperature heating, adds first modifying agent（Triethanolamine, oxidized starch, hydrogen peroxide are using weight ratio as 5:8:The mixing of 2 mixing
Thing）5kg, it is 9.0-9.5 to adjust reacting solution pH value using 25% sodium hydrate aqueous solution.When being warming up to 45 DEG C, stop heating,
Melamine 95kg is added, continues heating heating after addition；It is heated to stopping heating at 60 DEG C, is incubated 10 minutes.In 60-
The 1st crowd of urea 200kg of 65 DEG C of additions, it is F/U to make the mol ratio of formaldehyde and urea1=1.91, it is warming up to 75-85 DEG C and stops heating,
85-92 DEG C is warmed naturally to, is incubated 30 minutes.85-88 DEG C is cooled to, it is 6.0-6.8 to adjust pH value with 25% aqueous formic acid,
Polycondensation reaction is carried out at a temperature of 85-92 DEG C.Using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, when viscosity is the 16-18 seconds
When, it is first reaction end.After reaching first reaction end, reacting solution pH value is adjusted with 25% sodium hydrate aqueous solution
For 6.5-7.3, the 2nd crowd of urea 166kg is added, it is F/U to make the mol ratio of formaldehyde and urea2=1.18.The 2nd batch of urea 5 is added to divide
Zhong Hou, it is second reaction end when viscosity is the 18-20 seconds using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution.Add
Modifying agent（Triethanolamine, oxidized starch, hydrogen peroxide are using weight ratio as 5:8:The mixture of 2 mixing）15kg, use sodium hydroxide
Aqueous solution adjustment reacting solution pH value is 7.6-8.6, is incubated 10 minutes.Remaining urea 110kg is added, makes rubbing for formaldehyde and urea
Your ratio is F/U3=0.94, after being incubated 10 minutes, cool.38-43 DEG C is cooled to, pH value is adjusted extremely with sodium hydrate aqueous solution
7.5-8.6, discharging.
Embodiment 3
The formalin 730kg that mass percent concentration is 36.8%-37.2% is put into reactor, after stirring, risen
Temperature heating, adds first modifying agent（Diethylene glycol, oxidized starch, hydrogen peroxide, phenol are using weight ratio as 5:6:2:1 mixing
Mixture）6kg, it is 9.0-9.5 to adjust reacting solution pH value using 25% sodium hydrate aqueous solution.When being warming up to 45 DEG C, stop
Heating, melamine 168kg is added, continue heating heating after addition；It is heated to stopping heating at 60 DEG C, is incubated 10 points
Clock.The 1st crowd of urea 165kg is added at 60-65 DEG C, it is F/U to make the mol ratio of formaldehyde and urea1=1.92,85-92 DEG C is warming up to,
Insulation 30 minutes.In the case where temperature is 85-88 DEG C, it is 6.0-6.8 to adjust pH value with 25% aqueous formic acid, at a temperature of 85-92 DEG C
Carry out polycondensation reaction.Using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, when viscosity is the 16-18 seconds, for first reaction
Terminal.After reaching first reaction end, it is 6.8-7.5 to adjust reacting solution pH value with 25% sodium hydrate aqueous solution, adds the
2 crowdes of urea 171kg, it is F/U to make the mol ratio of formaldehyde and urea2=1.20.The 2nd batch of urea is added after 5 minutes, it is viscous using applying -4
The terminal of agar diffusion method detection reaction solution is spent, is second reaction end when viscosity is the 18-20 seconds.Add remaining modifying agent（Diethyl
Glycol, oxidized starch, hydrogen peroxide, phenol are using weight ratio as 5:6:2:The mixture of 1 mixing）14kg, it is water-soluble with sodium hydroxide
Liquid adjustment reacting solution pH value is 7.6-8.5, is incubated 10 minutes.Remaining urea 118kg is added, makes the mol ratio of formaldehyde and urea
For F/U3=0.96, after being incubated 10 minutes, cool.38-43 DEG C is cooled to, it is 8.0- to adjust pH value with sodium hydrate aqueous solution
8.5, discharging.
Embodiment 4
The formalin 620kg that mass percent concentration is 36.8% is put into reactor, after stirring, sampling detection
Concentration of formaldehyde, heating heating, adds first modifying agent（Triethanolamine, diethylene glycol, hydrogen peroxide are using weight ratio as 2:2:1
The mixture of mixing）5kg, the use of 25% sodium hydrate aqueous solution adjustment reacting solution pH value is 9.5.When being warming up to 45 DEG C, stop
Heating, melamine 52kg is added, continue heating heating after addition；It is heated to stopping heating at 60 DEG C, is incubated 10 minutes.
The 1st crowd of urea 207kg is added at 65 DEG C, it is F/U to make the mol ratio of formaldehyde and urea1=1.91, it is warming up to 85 DEG C and stops heating,
Insulation 30 minutes.It is 5.2 with 25% aqueous formic acid regulation pH value, polycondensation reaction is carried out at a temperature of 92 DEG C.Use -4 viscosity of painting
Agar diffusion method detects the terminal of reaction solution, is first reaction end when viscosity is the 16-18 seconds.After reaching first reaction end,
It is 6.5 with 25% sodium hydrate aqueous solution adjustment reacting solution pH value, adds the 2nd crowd of urea 153kg, make rubbing for formaldehyde and urea
Your ratio is F/U2=1.18.The 2nd batch of urea is added after 5 minutes, using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, works as viscosity
For the 18-20 seconds when, be second reaction end.Add remaining modifying agent（Triethanolamine, diethylene glycol, hydrogen peroxide are with weight
Than for 2:2:The mixture of 1 mixing）16kg, it is 8.5 with sodium hydrate aqueous solution adjustment reacting solution pH value, is incubated 10 minutes.
Remaining urea 121kg is added, it is F/U to make the mol ratio of formaldehyde and urea3=0.90, after being incubated 10 minutes, cool.Cooling
To 38 DEG C, pH value is adjusted to be discharged to 8.0 with sodium hydrate aqueous solution.
Detection obtains the adhesive performance such as following table of the preparation of embodiment 4（Wherein percentage is mass percent）：
It the above is only the feature implementation example of the present invention, the scope of the present invention be not limited in any way.It is all to use together
The technical scheme formed Deng exchange or equivalence replacement, all falls within rights protection scope of the present invention.
Claims (1)
- A kind of 1. Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive, it is characterised in that：Include the original of following parts by weight Material：Mass percent concentration be 36.8%-37.2% formalin 40-60 parts, urea 30-45 parts, melamine 5-25 parts, Modifying agent 1-10 parts；Described modifying agent is triethanolamine, diethylene glycol, hydrogen peroxide using weight ratio as 2:2:The mixture of 1 mixing；The preparation method of described Moisture-proof environment-friendlyshoe cyanurotriamide modified urea resin adhesive comprises the following steps：1) weighed by proportioning and formalin is put into reactor after each raw material, after stirring, add modifying agent gross weight 10%- 30% first modifying agent, it is 9.0-9.5 to adjust reacting solution pH value using sodium hydrate aqueous solution；2) reaction solution is heated to 45 DEG C, continues to be heated to 60-65 DEG C after adding melamine, be incubated 10-15 Minute；3) first urea is added, it is F/U to make the mol ratio of formaldehyde and urea1=1.85-2.05,85-92 DEG C is warming up to, insulation 25-35 minutes；4) it is 85-88 DEG C to adjust reaction solution temperature, and it is 4.8-6.8 to adjust pH value with aqueous formic acid, at a temperature of 85-92 DEG C Carry out polycondensation reaction；5) it is first reaction end when viscosity is the 16-18 seconds using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution；6) after reaching first reaction end, it is 5.8-7.5 to adjust reacting solution pH value with sodium hydrate aqueous solution, adds second Urea is criticized, it is F/U to make the mol ratio of formaldehyde and urea2=1.15-1.25；7) second batch urea is added after 5 minutes, using the terminal for applying -4 viscosity agar diffusion methods detection reaction solution, when viscosity is the 18-20 seconds When, it is second reaction end；8) remaining modifying agent is added, it is 7.6-8.8 to adjust reacting solution pH value with sodium hydrate aqueous solution, is incubated 10-15 minutes；9) the 3rd batch of urea is added, it is F/U to make the mol ratio of formaldehyde and urea3=0.88-0.97 is cold after being incubated 10-15 minutes But cool；10) 38-43 DEG C is cooled to, pH value is adjusted to 7.5-8.8, discharging with sodium hydrate aqueous solution.
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| CN106117476A (en) * | 2016-08-04 | 2016-11-16 | 广西三威林产工业有限公司 | High density fiberboard moistureproof adhesive and preparation method thereof |
| CN106883365B (en) * | 2017-02-23 | 2019-03-26 | 广州市长安粘胶制造有限公司 | A kind of E used for shaving board0Environment-friendly modified Lauxite of grade and preparation method thereof |
| CN108102057A (en) * | 2017-12-26 | 2018-06-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of outdoor stages environment-friendlymedium-density medium-density fiberboard adhesive |
| CN109824841A (en) * | 2018-12-31 | 2019-05-31 | 泉州市东紫环保科技有限公司 | A kind of preparation method of the Abietyl modified urea-formaldehyde resin adhesive of methylol |
| CN116199450A (en) * | 2023-02-02 | 2023-06-02 | 佳诺威集团股份有限公司 | Composite modifier for urea-formaldehyde resin adhesive |
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| DE102004025442A1 (en) * | 2004-05-19 | 2005-12-22 | Basf Ag | Aminoplast resin for the production of binders |
| CN100572445C (en) * | 2007-09-17 | 2009-12-23 | 中国林业科学研究院木材工业研究所 | A kind of preparation method of modified urea-formaldehyde resin |
| CN102775946B (en) * | 2012-07-18 | 2014-01-01 | 广西华峰林业股份有限公司 | MDF(Medium-density fiber)-E1-level urea-formaldehyde resin adhesive |
| CN103045140B (en) * | 2012-12-13 | 2014-07-02 | 佛山市天元汇邦装饰材料有限公司 | Low formaldehyde resin adhesive for decorative impregnating paper and preparation method thereof |
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Address after: 343100 Ji'an City, Jiangxi Province Economic and Technological Development Zone Jinggangshan Ji Tai Road No. 29 Applicant after: Jiangxi Oasis Environmental Protection new material Limited by Share Ltd Address before: 343100 Ji'an City, Jiangxi Province Economic and Technological Development Zone Jinggangshan Ji Tai Road No. 29 Applicant before: Jiangxi Lvzhou Artificial Board Co., Ltd. |
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Address after: 343100 No. 29 Jitai Road, Jinggangshan Economic and Technological Development Zone, Ji'an County, Ji'an City, Jiangxi Province Patentee after: Jiangxi Oasis Environmental Protection New Materials Co., Ltd. Address before: 343100 No. 29 Jitai Road, Jinggangshan Economic and Technological Development Zone, Ji'an City, Jiangxi Province Patentee before: Jiangxi Oasis Environmental Protection new material Limited by Share Ltd |
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