CN104762041B - Modified urea resin adhesive and preparation method thereof - Google Patents
Modified urea resin adhesive and preparation method thereof Download PDFInfo
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- CN104762041B CN104762041B CN201510134976.2A CN201510134976A CN104762041B CN 104762041 B CN104762041 B CN 104762041B CN 201510134976 A CN201510134976 A CN 201510134976A CN 104762041 B CN104762041 B CN 104762041B
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Abstract
The invention discloses a modified urea resin adhesive and a preparation method thereof. According to the preparation method, formaldehyde and urea in a low molar ratio are taken as raw materials, and a poly-functionality reaction enhancer is taken as a polycondensation agent to replace an acidic polycondensation condition, and the urea resin is synthesized by use of an acid-alkali-acid process; the molecular branching coefficient of the urea resin is increased, the molecular weight of the urea resin is increased under the same viscosity, and the curing cross-linking density of the urea resin can be increased, and furthermore, the bonding strength is improved and the formaldehyde release amount of the bonded products is reduced. The preparation method of the low-toxicity urea resin adhesive has the advantages that non-traditional melamine-epoxy chloropropane-sodium hydroxide reactants are taken as polycondensation agents and the acid-alkali-acid synthesis process is adopted, the basic procedure is close to the conventional process, the process is simple, the operations are convenient, and the existing equipment does not need to be modified.
Description
Technical field
The present invention relates to a kind of adhesive, specifically a kind of modified urea-formaldehyde resin adhesive for preparing wood-based plate
And preparation method thereof, belong to adhesive area.
Background technology
With the raising and the sustainable and stable development of the industry such as building, decorations, packaging of living standards of the people, Chinese people
Make plate yield to increase rapidly.Wood-based plate total output, glued board yield, furniture yield, wood floors yield occupy generation for years
Boundary is the first.2013, the m3 of China wood-based plate total output 2.72 hundred million accounted for the 50% of Gross World Product.Averagely give birth to by adhesive per ton
Produce 9m3 wood-based plates to calculate, about 30,000,000 tons of China wood adhesive consumption in 2013（Solids content 50%）, wherein ureaformaldehyde tree
Fat and its modified product account for more than the 80% of adhesive total output, occupy an leading position.Why urea-formaldehyde resin adhesive can be in timber
Use in a large number in industry, be that such as raw material is sufficient, cheap, water-soluble because it has the incomparable advantage of other resins
The good, glue-line of property is of light color etc..But Lauxite also has some significantly shortcomings, except resistance to ag(e)ing is poor, poor water resistance, no
Can be used to prepare outside outdoor use wood-based plate, its fatal shortcoming is that the wood-based plate being glued has Form aldehyde release.With people
Quality of life is improved, and health and environmental consciousness strengthen, and people increasingly mainly arrive urea-formaldehyde resin adhesive and preparing and using
Cheng Zhonghui releases formaldehyde, and it is glued wood-based plate also can constantly discharge formaldehyde during use, pollutes human settlement, infringement
People are healthy.
At present, the method for reducing artificial board formaldehyde burst size mainly has following 4 kinds：1）Using low mole prop0rtion modified urea-formaldehyde tree
Fat adhesive；2）Formaldehyde catching agent is added in modified urea-formaldehyde resin adhesive；3）Wood-based plate is post-processed；4）Using it
His environmental-protection type adhesive.But, these technical methods all have many defects.For example：1）Using low mole prop0rtion modified urea-formaldehyde
Although resin adhesive can effectively reduce wood-based panel product burst size of methanal, product bonding strength also tends to reduce, no
Use requirement can be met；And hardening time can be caused to extend, production efficiency is reduced；2）In urea-formaldehyde resin for artificial board adhesive
Middle addition formaldehyde catching agent, although can effectively reduce free formaldehyde in artificial plate burst size, but often reduce wood-based plate simultaneously
Bonding strength；Meanwhile, general formaldehyde catching agent price often be significantly larger than urea-formaldehyde resin adhesive, its addition improve product into
This, reduces product competitiveness；3）Wood-based plate is post-processed, such as in the application for a patent for invention of Publication No. CN1526528
Disclose the manufacturing process that a kind of employing ammonia vacuum method prepares E1/EO level environment friendly artificial boards；Publication No. CN2394770
A kind of processing meanss of reduction artificial board formaldehyde burst size are disclosed in utility model patent, these post-processing approach not only make
Obtain wood-based plate manufacturing process complicated, and equipment for after-treatment investment is huge, and production cost is significantly improved；4）Using other environment-friendly types
Adhesive, such as isocyanates adhesive, cause Wood-based Panel Production cost to increase considerably, producting process difficulty increase, enterprise
All it is difficult to receive with user；Wood-based plate bonding strength is prepared using general proteins adhesive low, water resistance is poor, easily mouldy, apply
Glue poor performance, wood-based plate easily come unglued.In sum, although above-mentioned measure can effectively reduce free formaldehyde in artificial plate burst size,
But Form aldehyde release can not be thoroughly solved the problems, such as, or cannot be promoted due to excessively high etc. reason of production cost.
The content of the invention
In order to solve the above problems, the present invention devises a kind of modified urea-formaldehyde resin adhesive and preparation method thereof, adopts
The formaldehyde and urea of low mole prop0rtion is raw material, and using the agent of polyfunctionality increased response as polycondensation agent acid polycondensation condition is substituted,
Synthesize Lauxite with " Acid-Base-acid " technique, improve Lauxite branchign of molecule degree, ureaformaldehyde tree is increased under identical viscosities
Fat molecular weight, it is possible to increase Lauxite solidifies crosslink density, and then improves glue-joint strength, reduces cementitious article Form aldehyde release
Amount, process is simple, operation facility, and solve the problems, such as raw material resources.
The technical scheme is that：
A kind of modified urea-formaldehyde resin adhesive, is prepared from by formaldehyde, urea, polyvinyl alcohol and increased response agent, wherein,
The increased response agent is melamine-epoxychloropropane-NaOH reactant, and the mol ratio of described Jia Quan ︰ urea is
1.1-0.95, the polyvinyl alcohol accounts for the 0.1-0.8% of gross weight, and the increased response agent accounts for the 0.5-5.0% of gross weight.
Preferably, the mol ratio of described Jia Quan ︰ urea is 1.07-0.98；The polyvinyl alcohol accounts for the 0.3- of gross weight
0.5%；The increased response agent accounts for the 1-3.0% of gross weight.
Wherein, the increased response agent is melamine-epoxychloropropane-NaOH reactant, and preparation method is：Will
1mol melamines and 10mol water are placed in four-hole boiling flask constant temperature to 60 DEG C, add the sodium hydroxide solution of 0.15mol as urging
Agent, is then slowly dropped into the epoxychloropropane monomer of 6mol and reacts 5 hours at 50-80 DEG C, after be cooled to 40 DEG C, add
0.15mol NaOH, stirs 1 hour, neutralizes unnecessary alkali, rotates free epoxychloropropane, after drying, obtains the present invention
Increased response agent.
A kind of preparation method of above-mentioned modified urea-formaldehyde resin adhesive, including following preparation steps：
1）Formaldehyde is put in reactor, first urea is added, makes formaldehyde be 2.0-2.2 with urea mol ratio:1, adjust
It is 6.0 to save pH value, and at 60 DEG C 20 minutes are incubated, and 90 DEG C are warming up in 20 minutes, keeps PH5.5-6.0, insulation to add after 20 minutes
Enter poly-vinyl alcohol solution, be incubated 30 minutes；
2）Control ph is 7-9, adds increased response agent, control temperature to react to viscosity at 85-90 DEG C by several times：25 DEG C,
- 4 glasss of 22-24 seconds are applied, second batch urea is added, makes formaldehyde be 1.4-1.2 with urea mol ratio:1, regulation pH value is 7-9, is added dropwise
Increased response agent, reacts to viscosity：25 DEG C, -4 glasss of 24-26 seconds are applied, regulation pH value is 6.0-7.0；
3）The 3rd batch of urea is added, makes formaldehyde be 0.95-1.1 with urea mol ratio:1, to react 30 minutes, 40 DEG C of cooling goes out
Material.
Wherein, the formaldehyde is the formalin of mass concentration 36.5-37.5%；The alkali that regulation pH value is used is selected from hydrogen-oxygen
Change one or more mixing in sodium, sodium carbonate, triethanolamine；The acid that regulation pH value is used is selected from formic acid, acetic acid, chlorination
One or more mixing in ammonium, citric acid.
Wherein, the increased response agent is melamine-epoxychloropropane-NaOH reactant, and preparation method is：Will
1mol melamines and 10mol water are placed in four-hole boiling flask constant temperature to 60 DEG C, add the sodium hydroxide solution of 0.15mol as urging
Agent, is then slowly dropped into the epoxychloropropane monomer of 6mol and reacts 5 hours at 50-80 DEG C, after be cooled to 40 DEG C, add
0.15mol NaOH, stirs 1 hour, neutralizes unnecessary alkali, rotates free epoxychloropropane, after drying, obtains the present invention
Increased response agent.
It is an advantage of the current invention that：
1）The present invention uses melamine-epoxychloropropane-NaOH reactant to substitute acid polycondensation as polycondensation agent
Condition, with " Acid-Base-acid " technique Lauxite is synthesized, and improves Lauxite branchign of molecule degree, and tree is increased under identical viscosities
Fat molecular weight, improves resin solidification crosslink density, forms Lauxite and stablize in a large number chemical bond, makes formaldehyde/urea mole
Than in 0.95-1.1:The glued board that 1 Lauxite is produced, with very high bonding strength and extremely low burst size of methanal；
2）Using unconventional melamine-epoxychloropropane-NaOH reactant as polycondensation in the inventive method
Agent and " Acid-Base-acid " synthesis technique coordinate, and basic procedure is close to conventional process, process is simple, operation facility, without to existing
There is equipment to be transformed.
With reference to specific embodiment, the invention will be further described.
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Unless otherwise stated, the percentage employed in the present invention is percetage by weight.
Embodiment 1
A kind of modified urea-formaldehyde resin adhesive, composition of raw materials see the table below 1：
The formaldehyde of table 1 is 1.07 with urea mol ratio:1 Lauxite raw material proportioning：
A kind of preparation method of above-mentioned modified urea-formaldehyde resin adhesive, gets the raw materials ready, instead with urea mol ratio by formaldehyde for 1.07
Step is answered to include：
1）The weight portion of 37% industrial formol 591.2 is put in reactor, first weight portion of urea 208.3 is added, is adjusted
PH value is 6.0, and at 60 DEG C 20 minutes are incubated, and 90 DEG C are warming up in 20 minutes, keeps PH5.5-6.0, is warming up to 90 DEG C, insulation 20
The weight portion of poly-vinyl alcohol solution 30 is added after minute, 20 minutes are incubated；
2）Control ph is 7-9, adds the weight portion of increased response agent 5 by several times, and control temperature is reacted to viscous at 85-90 DEG C
Degree：25 DEG C, -4 glasss of 22-24 seconds are applied, add the weight portion of second batch urea 128.2, regulations pH value is 7-9, dropwise reaction reinforcing agent 7
Weight portion, reacts to viscosity：25 DEG C, -4 glasss of 24-26 seconds are applied, regulation pH value is 6.0-7.0；
3）The 3rd batch of weight portion of urea 72.3 is added, is reacted 30 minutes, 40 DEG C of dischargings of lowering the temperature.
As a result, resin quality index, see the table below：
Comparative example 1（Without increased response agent）
A kind of modified urea-formaldehyde resin adhesive, composition of raw materials see the table below 2
The formaldehyde of table 2 is 1.07 with urea mol ratio:1 Lauxite raw material proportioning：
A kind of preparation method of above-mentioned modified urea-formaldehyde resin adhesive, gets the raw materials ready, instead with urea mol ratio by formaldehyde for 1.07
Step is answered to include：
1）The weight portion of 37% industrial formol 591.2 is put in reactor, the weight portion of poly-vinyl alcohol solution 3 is added, alkali lye is used
It is 8.0 to adjust pH value, adds first weight portion of urea 208.3, and 90 DEG C are warming up in 1 hour, is incubated 1 hour, keeps pH value
For 7.5-8.0；
2）It is 3.4-4.2 with acid solution control ph, reacts to viscosity at 95 DEG C：25 DEG C, -4 glasss of 24-27 seconds are applied, add the
Two batches of weight portions of urea 128.2, are incubated 30 minutes, and it is 7.5-8.0 to adjust pH value with alkali lye；
3）The 3rd batch of weight portion of urea 72.3 is added, is reacted 30 minutes, lowered the temperature 35 DEG C, it is 7.5- to adjust pH value with alkali lye
8.0, discharging.
As a result, resin quality index, resin quality index see the table below：
Interpretation of result：From above-described embodiment as can be seen that the product containing increased response agent, its performance indications is substantially better than
Properties of product without increased response agent.
Embodiment 2
A kind of modified urea-formaldehyde resin adhesive, composition of raw materials see the table below 3：
The formaldehyde of table 3 is 1 with urea mol ratio:0.98 Lauxite raw material proportioning：
A kind of preparation method of above-mentioned modified urea-formaldehyde resin adhesive, is 1 by formaldehyde and urea mol ratio:0.98 gets the raw materials ready,
Reactions steps include：
1）The weight portion of 37% industrial formol 569.8 is put in reactor, first weight portion of urea 210.8 is added, is adjusted
PH value is 6.0, and at 60 DEG C 20 minutes are incubated, and 90 DEG C are warming up in 20 minutes, keeps PH5.5-6.0, is warming up to 90 DEG C, insulation 20
The weight portion of poly-vinyl alcohol solution 50 is added after minute, 20 minutes are incubated；
2）Control ph is 7-9, and the weight portion of dropwise reaction reinforcing agent 8, control temperature is reacted to viscosity at 85-90 DEG C：25
DEG C, -4 glasss of 22-24 seconds are applied, add the weight portion of second batch urea 140.5, regulations pH value is 7-9, the weight of dropwise reaction reinforcing agent 10
Part, react to viscosity：25 DEG C, -4 glasss of 24-26 seconds are applied, regulation pH value is 6.0-7.0；
3）The 3rd batch of weight portion of urea 78.9 is added, is reacted 30 minutes, 40 DEG C of dischargings of lowering the temperature.
As a result, resin quality index, see the table below：
Comparative example 2（Without increased response agent）
A kind of modified urea-formaldehyde resin adhesive, composition of raw materials see the table below 4
The formaldehyde of table 4 is 1 with urea mol ratio:0.98 Lauxite raw material proportioning：
A kind of preparation method of above-mentioned modified urea-formaldehyde resin adhesive, is 1 by formaldehyde and urea mol ratio:0.98 gets the raw materials ready,
Reactions steps include：
1）The weight portion of 37% industrial formol 569.8 is put in reactor, the weight portion of poly-vinyl alcohol solution 5 is added, alkali lye is used
It is 8.0 to adjust pH value, adds first weight portion of urea 210.8, and 90 DEG C are warming up in 1 hour, is incubated 1 hour, keeps pH value
For 7.5-8.0；
2）It is 3.4-4.2 with acid solution control ph, reacts to viscosity at 95 DEG C：25 DEG C, -4 glasss of 24-27 seconds are applied, add the
Two batches of weight portions of urea 140.5, are incubated 30 minutes, and it is 7.5-8.0 to adjust pH value with alkali lye；
3）The 3rd batch of weight portion of urea 78.9 is added, is reacted 30 minutes, lowered the temperature 35 DEG C, it is 7.5- to adjust pH value with alkali lye
8.0, discharging.
As a result, resin quality index, resin quality index see the table below：
Interpretation of result：From above-described embodiment as can be seen that the product containing increased response agent, its performance indications is substantially better than
Properties of product without increased response agent.
Experimental example
The Lauxite of above-described embodiment and comparative example is separately added into into 0.6% ammonium chloride and 0.4% citric acid, is added afterwards
32% flour manufactures three layers of 400 × 400mm glued boards.
Board using poplar board：Moisture content is dried to 10-14%；Thick 1.5mm；
Veneer adhesive is using the product of embodiment of the present invention 1-2 and the product of comparative example 1-2.
Glued board is prepared by following normal process：
Applying glue：The two-sided applying glue of central layer, glue-spread is 300-320g/m2；
Aging and time：Closure ageing, 20-30 minutes；
Preload pressure and time：Precompressed 40 minutes, pressure 0.9MPa；
Hot pressing pressure：1.0MPa, hot pressing temperature is 110-120 DEG C, and hot pressing time is 60s/mm.
By GB/T17657-1999《Wood-based plate and face artificial board physicochemical property experimental technique》Detection method is to production
Plywood product carries out performance detection, and testing result is shown in Table 5.
Table 5 is glued the burst size of methanal and bonding strength of glued board
Interpretation of result：By above-mentioned test result indicate that, the modified urea-formaldehyde resin prepared using the present invention can effectively be dropped
Low glued board burst size of methanal, improves water-fast bonding property, reaches II classes glued board standard in GB（Poplar >=0.70MPa）.
Raw materials used being in the production of this area commonly uses raw material in the present invention, can obtain from market, and for production
As a result impact will not be produced；Various equipment employed in the present invention, the conventional equipment being used in the production technology of this area,
And operation, the parameter of each equipment etc. is carried out according to routine operation, special feature is had no.
Claims (5)
1. a kind of modified urea-formaldehyde resin adhesive, it is characterised in that：Prepared by formaldehyde, urea, polyvinyl alcohol and increased response agent
Form, wherein, the increased response agent be melamine-epoxychloropropane-NaOH reactant, described Jia Quan ︰ urea
Mol ratio be 1.1-0.95, the polyvinyl alcohol accounts for the 0.1-0.8% of gross weight, and the increased response agent accounts for gross weight
0.5-5.0%；
The increased response agent is melamine-epoxychloropropane-NaOH reactant, and preparation method is：By 1mol trimerizations
Cyanamide and 10mol water are placed in four-hole boiling flask constant temperature to 60 DEG C, add the sodium hydroxide solution of 0.15mol as catalyst, so
Be slowly dropped into the epoxychloropropane monomer of 6mol afterwards to react 5 hours at 50-80 DEG C, after be cooled to 40 DEG C, add 0.15mol hydrogen-oxygens
Change sodium, stir 1 hour, neutralize unnecessary alkali, rotate free epoxychloropropane, obtain after drying.
2. a kind of modified urea-formaldehyde resin adhesive according to claim 1, it is characterised in that：Described Jia Quan ︰ urea
Mol ratio is 1.07-0.98.
3. a kind of modified urea-formaldehyde resin adhesive according to claim 1, it is characterised in that：The polyvinyl alcohol is accounted for always
The 0.3-0.5% of weight.
4. a kind of modified urea-formaldehyde resin adhesive according to claim 1, it is characterised in that：The increased response agent is accounted for
The 1-3.0% of gross weight.
5. a kind of preparation method of a kind of modified urea-formaldehyde resin adhesive as described in claim 1-4 any one, its feature
It is, including following preparation steps：
1）Formaldehyde is put in reactor, first urea is added, makes formaldehyde be 2.0-2.2 with urea mol ratio:1, adjust pH
It is worth for 6.0, at 60 DEG C 20 minutes is incubated, 90 DEG C are warming up in 20 minutes, keeps pH5.5-6.0, insulation to add poly- after 20 minutes
Glycohol solution, is incubated 30 minutes；
2）Control ph is 7-9, adds increased response agent, control temperature to react to viscosity at 85-90 DEG C by several times：25 DEG C, apply -4
The cup 22-24 seconds, second batch urea is added, make formaldehyde be 1.4-1.2 with urea mol ratio:1, regulation pH value be 7-9, dropwise reaction
Reinforcing agent, reacts to viscosity：25 DEG C, -4 glasss of 24-26 seconds are applied, regulation pH value is 6.0-7.0；
3）The 3rd batch of urea is added, makes formaldehyde be 0.95-1.1 with urea mol ratio:1, react 30 minutes, 40 DEG C of dischargings of lowering the temperature；
The formaldehyde is the formalin of mass concentration 36.5-37.5%；The alkali that regulation pH value is used is selected from NaOH, carbonic acid
One or more mixing in sodium, triethanolamine；The acid that regulation pH value is used is in formic acid, acetic acid, ammonium chloride, citric acid
One or more mixing；
The increased response agent is melamine-epoxychloropropane-NaOH reactant, and preparation method is：By 1mol trimerizations
Cyanamide and 10mol water are placed in four-hole boiling flask constant temperature to 60 DEG C, add the sodium hydroxide solution of 0.15mol as catalyst, so
Be slowly dropped into the epoxychloropropane monomer of 6mol afterwards to react 5 hours at 50-80 DEG C, after be cooled to 40 DEG C, add 0.15mol hydrogen-oxygens
Change sodium, stir 1 hour, neutralize unnecessary alkali, rotate free epoxychloropropane, obtain after drying.
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| CN201510134976.2A CN104762041B (en) | 2015-03-26 | 2015-03-26 | Modified urea resin adhesive and preparation method thereof |
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| CN108582347B (en) * | 2018-05-02 | 2020-07-07 | 浙江龙达实业股份有限公司 | Modified wood and preparation method thereof |
| CN112625584A (en) * | 2020-12-03 | 2021-04-09 | 安徽嘉明新材料科技有限公司 | Preparation method and application of TPU coating with good adhesion performance |
| CN116284652B (en) * | 2023-03-10 | 2023-08-08 | 河北乾海管道制造有限公司 | Steel sleeve steel polyurethane heat-insulating pipe and preparation method thereof |
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| CN100582135C (en) * | 2007-05-25 | 2010-01-20 | 北京化工大学 | Method for preparing post-crosslinking modified urea-formaldehyde resin adhesive |
| EP2548978A1 (en) * | 2011-07-21 | 2013-01-23 | Clariant S.A., Brazil | Binder composition for the agglomeration of fine minerals and pelletizing process using the same |
| CN102827366A (en) * | 2012-07-20 | 2012-12-19 | 上海谊和环保材料有限公司 | Polymeric adsorbent for removing formaldehyde and preparation method thereof |
| CN103570975A (en) * | 2013-11-18 | 2014-02-12 | 闽江学院 | Nitrogen-phosphorus composite flame retardant as well as preparation method and application thereof |
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