CN106753104A - A kind of urea-formaldehyde resin adhesive and its preparation method and application - Google Patents
A kind of urea-formaldehyde resin adhesive and its preparation method and application Download PDFInfo
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- CN106753104A CN106753104A CN201611171313.9A CN201611171313A CN106753104A CN 106753104 A CN106753104 A CN 106753104A CN 201611171313 A CN201611171313 A CN 201611171313A CN 106753104 A CN106753104 A CN 106753104A
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- urea
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
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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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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a kind of urea-formaldehyde resin adhesive, prepared by the raw material comprising following mass fraction：0.5~5 part of 100 parts of urea, 50~60 parts of formaldehyde, 5~20 parts of water, 0.5~3 part of coupling agent, 0.5~2 part of polyethylene glycol and lignin.The urea-formaldehyde resin adhesive that the present invention is provided ensure that by the mechanical property of bonding product while burst size of methanal is reduced.The urea-formaldehyde resin adhesive that the present invention is provided is creamy white, and the content of the aldehyde that dissociates is less than 0.12%, and solid content is 41~58%, and viscosity is 17~30S.In addition, the MOR of sheet material prepared by the urea-formaldehyde resin adhesive that the present invention is provided is 20.1~28.9MPa, and elastic modelling quantity is 1689~2635MPa, and internal bond strength is 0.39~0.58MPa, thickness swelling rate is 5.1~9.5%, and burst size of methanal is 0.11~0.42mg/L.
Description
Technical field
The present invention relates to organic material technical field, more particularly to a kind of urea-formaldehyde resin adhesive and preparation method thereof and should
With.
Background technology
Acted on cohesion etc. by sticking for interface, can make what two or more product or material linked together
Natural or synthesis a, organic or inorganic class material, is referred to as adhesive.With growing stronger day by day for wood-based panel industry,
Wood composite material is widely used in the fields such as house construction and household.For Wood composite material, the use of adhesive
It is essential.
However, being widely used in the big back ofs the body closely bound up with human lives such as house construction and household in Wood composite material
Under scape, adhesive used still based on three formaldehyde resins, i.e. urea-formaldehyde resin adhesive, phenolic resin adhesive and melamine tree
Fat adhesive.Product prepared by three-aldehyde glue has lasting Form aldehyde release problem, and formaldehyde is potential carcinogenic substance, is threaten
The health of the mankind.
In order to adapt to product environmental performance requirement, existing most of artificial liner enterprises all using low aldehyde urea than Lauxite it is gluing
Agent prescription or modified urea-formaldehyde resin formula are produced.However, the mechanical property that these adjustment bond product to it can be produced
Influence.
The content of the invention
It is an object of the invention to provide a kind of urea-formaldehyde resin adhesive and its preparation method and application.What the present invention was provided
Urea-formaldehyde resin adhesive ensure that by the mechanical property of bonding product while burst size of methanal is reduced.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of urea-formaldehyde resin adhesive, prepared by the raw material comprising following mass fraction：
Preferably, the lignin is in Milled wood lignin, Corn cob lignin, bamboo matter lignin and straw lignin
One or more.
Preferably, the coupling agent is polyisocyanates and/or organo-silicon coupling agent.
Present invention also offers a kind of preparation method of urea-formaldehyde resin adhesive described in above-mentioned technical proposal, comprising following step
Suddenly：
The first polycondensation reaction is carried out after formaldehyde, water, first part of urea, coupling agent and polyethylene glycol are mixed, first is obtained
Condensation polymer；
The pH value of first condensation polymer is adjusted for after 6~6.5, mixing with second part of urea and lignin carries out the second contracting
Poly- reaction, obtains the second condensation polymer；
The pH value of second condensation polymer is adjusted after 7.5~8, the polycondensation reaction of row the 3rd to be mixed into remaining urea, is obtained
To the 3rd condensation polymer；
It is 7~7.5 to adjust the pH value of the 3rd condensation polymer, obtains urea-formaldehyde resin adhesive.
Preferably, the temperature of first polycondensation reaction is 90~95 DEG C；
The time of first polycondensation reaction is 20~40 minutes.
Preferably, the temperature of second polycondensation reaction is 90~95 DEG C；
The time of second polycondensation reaction is 20~40 minutes.
Preferably, the temperature of the 3rd polycondensation reaction is 80~90 DEG C；
The time of the 3rd polycondensation reaction is 20~40 minutes.
Preferably, the mass ratio of first part of urea, second part of urea and remaining urea is (50~60):(20~
25):(20~25).
Made present invention also offers described in urea-formaldehyde resin adhesive described in a kind of above-mentioned technical proposal or above-mentioned technical proposal
The application of the urea-formaldehyde resin adhesive that Preparation Method is obtained, as the gluing of fiberboard, particieboard, woodwork plate and bamboo-wood plywood
Agent.
The invention provides a kind of urea-formaldehyde resin adhesive, prepared by the raw material comprising following mass fraction：Urea
0.5~5 part of 100 parts, 50~60 parts of formaldehyde, 5~20 parts of water, 0.5~3 part of coupling agent, 0.5~2 part of polyethylene glycol and lignin.
The urea-formaldehyde resin adhesive that the present invention is provided ensure that by the mechanical property of bonding product while burst size of methanal is reduced.
It can be seen from experimental result according to embodiment, the urea-formaldehyde resin adhesive that the present invention is provided is creamy white, and the content of free aldehyde is less than
0.12%, solid content is 41~58%, and viscosity is 17~30S；Plate prepared by the urea-formaldehyde resin adhesive provided using the present invention
The MOR of material be 20.1~28.9MPa, elastic modelling quantity be 1689~2635MPa, internal bond strength be 0.39~
0.58MPa, thickness swelling rate is 5.1~9.5%, and burst size of methanal is 0.11~0.42mg/L.
Present invention also offers a kind of preparation method of urea-formaldehyde resin adhesive described in above-mentioned technical proposal, comprising following step
Suddenly：The first polycondensation reaction is carried out after formaldehyde, water, first part of urea, coupling agent and polyethylene glycol are mixed, the first polycondensation is obtained
Thing；To carry out the second polycondensation anti-after 6~6.5, to mix with second part of urea and lignin to adjust the pH value of first condensation polymer
Should, obtain the second condensation polymer；The pH value of second condensation polymer is adjusted after 7.5~8, the contracting of row the 3rd to be mixed into remaining urea
Poly- reaction, obtains the 3rd condensation polymer；It is 7~7.5 to adjust the pH value of the 3rd condensation polymer, obtains urea-formaldehyde resin adhesive.This
That invents that the preparation method for providing enables to that the reaction of each step carries out is very abundant, can to greatest extent consume first
Aldehyde, and then reduce the content of formaldehyde in final product.
Specific embodiment
The invention provides a kind of urea-formaldehyde resin adhesive, prepared by the raw material comprising following mass fraction：
In the present invention, the raw material of urea-formaldehyde resin adhesive is prepared on the basis of the amount of urea, comprising 100 parts of urea.This
Invention, to the no particular/special requirement in source of the urea, can be specifically commercially available urea.In the present invention, the urea
Purity is preferred >=and 98%, preferred >=98.5%, most preferably >=99%.
On the basis of 100 parts of urea, the raw material that the present invention prepares urea-formaldehyde resin adhesive includes 50~60 parts of formaldehyde, preferably
It is 52~58 parts, more preferably 54~56 parts.In the present invention, the formaldehyde is preferably added in the form of formalin,
More preferably formalin, the mass fraction of the formaldehyde is calculated with the formaldehyde in formalin.In the present invention, it is described
The mass concentration of formalin is preferably 35~40%, more preferably 36~39%, most preferably 37~38%.
On the basis of 100 parts of urea, the raw material that the present invention prepares urea-formaldehyde resin adhesive includes 5~20 parts of water, preferably
10~18 parts, more preferably 12~15 parts.The present invention is not particularly limited to the source of the water, can be specifically deionization
Water, distilled water, pure water or running water.
On the basis of 100 parts of urea, the raw material that the present invention prepares urea-formaldehyde resin adhesive includes 0.5~3 part of coupling agent, excellent
Elect 1~2.5 part, more preferably 1.5~2 parts as.In the present invention, the coupling agent is preferably polyisocyanates and/or organic
Silicone couplet.In the present invention, the polyisocyanates is preferably diisocyanate and/or triisocyanate.In the present invention,
The organo-silicon coupling agent is preferably gamma-aminopropyl-triethoxy-silane (KH550), γ-glycidyl ether oxygen propyl trimethoxy
Base silane (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), N- (β-aminoethyl)-γ-aminopropyl
Trimethoxy silane (KH792), N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (DL602) and vinyl front three
One or more in TMOS (DL171).In the present invention, when the coupling agent is that polyisocyanates and organosilicon are coupled
During the mixture of agent, the two can be mixed according to arbitrary ratio.
On the basis of 100 parts of urea, the raw material that the present invention prepares urea-formaldehyde resin adhesive includes 0.5~2 part of polyethylene glycol,
Preferably 0.8~1.8 part, more preferably 1~1.5 part.The no particular/special requirement in source to the polyethylene glycol of the invention, specifically
Can be commercially available polyethylene glycol.The present invention does not have particular/special requirement to the specification of the polyethylene glycol, using art technology
Polyethylene glycol known to personnel.In the present invention, the polyethylene glycol is preferably polyethylene glycol 200, polyethylene glycol
400th, one or more in Macrogol 600, polyethylene glycol-800, cetomacrogol 1000 and polyethylene glycol 1500.
On the basis of 100 parts of urea, the raw material that the present invention prepares urea-formaldehyde resin adhesive includes 0.5~5 part of lignin, excellent
Elect 1~4 part, more preferably 2~3 parts as.In the present invention, the lignin be preferably Milled wood lignin, Corn cob lignin,
One or more in bamboo matter lignin and straw lignin.The present invention is not particularly limited to the source of the lignin, has
Body can be the lignin of commercially available mentioned kind, such as papermaking paper oar black liquid extraction lignin.The present invention is to the papermaking
The extracting method of paper oar black liquid extraction lignin does not have particular/special requirement, using apparatus and method well-known to those skilled in the art
Extracted.
The invention provides a kind of preparation method of urea-formaldehyde resin adhesive described in above-mentioned technical proposal, comprising following step
Suddenly：
The first polycondensation reaction is carried out after formaldehyde, water, first part of urea, coupling agent and polyethylene glycol are mixed, first is obtained
Condensation polymer；
The pH value of first condensation polymer is adjusted for after 6~6.5, mixing with second part of urea and lignin carries out the second contracting
Poly- reaction, obtains the second condensation polymer；
The pH value of second condensation polymer is adjusted after 7.5~8, the polycondensation reaction of row the 3rd to be mixed into remaining urea, is obtained
To the 3rd condensation polymer；
It is 7~7.5 to adjust the pH value of the 3rd condensation polymer, obtains urea-formaldehyde resin adhesive.
The present invention carries out the first polycondensation reaction after mixing formaldehyde, water, first part of urea, coupling agent and polyethylene glycol, obtains
To the first condensation polymer.It is currently preferred first to mix formaldehyde and water, then again with first part of urea, coupling agent and polyethylene glycol
Mixing.Before mixing with first part of urea, coupling agent and polyethylene glycol, the mixture of currently preferred regulation formaldehyde and water
PH value is 8.5~9, more preferably 8.6~8.9, most preferably 8.7~8.8.
The present invention does not have particular/special requirement to the material for adjusting the mixture ph of the formaldehyde and water, using art technology
Inorganic alkali lye known to personnel.In the present invention, the inorganic alkali lye is preferably sodium hydroxide solution and/or hydroxide
Potassium solution.The present invention does not have any particular/special requirement to the concentration of the inorganic alkali lye, is capable of the pH of the mixture of PARA FORMALDEHYDE PRILLS(91,95) and water
Value is adjusted.The pH value of the mixture of present invention regulation formaldehyde and water is that 8.5~9 can slow down the anti-of formaldehyde and urea
Answer speed so that it is more abundant that the first polycondensation reaction is carried out.
In the present invention, the temperature of first polycondensation reaction is preferably 90~95 DEG C, more preferably 91~94 DEG C, optimal
Elect 92~93 DEG C as；The time of first polycondensation reaction is preferably 20~40 minutes, more preferably 25~35 minutes, most preferably
It is 28~33 minutes
It is currently preferred to be started to warm up from room temperature to the temperature of the first polycondensation reaction.It is anti-that the present invention is warming up to the first polycondensation
The heating rate of temperature is answered to be controlled preferably through the heating-up time；The heating-up time is preferably 40~45 minutes, more excellent
Elect 41~44 minutes, most preferably 42~43 minutes as.
After obtaining the first condensation polymer, the pH value of present invention regulation first condensation polymer for after 6~6.5, with second part of urine
Element and lignin mixing carry out the second polycondensation reaction, obtain the second condensation polymer.The pH value of present invention regulation first condensation polymer
It is 6~6.5, preferably 6.1~6.4, more preferably 6.2~6.3.Material of the present invention to regulation the first condensation polymer pH value
There is no particular/special requirement, using inorganic acid well-known to those skilled in the art or organic acid.In the present invention, the nothing
Machine acid is preferably hydrochloric acid, sulfuric acid or nitric acid；The organic acid is preferably formic acid or acetic acid.It is of the invention to the inorganic acid and organic
The concentration of acid does not have any particular/special requirement, and the pH value of the first condensation polymer can be adjusted.
Regulation of the present invention to the first condensation polymer pH value is preferably divided into four-stage：First stage, second stage,
Phase III and fourth stage.In the present invention, the first stage preferably adjust the pH value of first condensation polymer for 5.8~
6, can be specifically 5.8,5.9 or 6.In the present invention, the interval time of the first stage and second stage be preferably 8~
10 minutes, can be specifically 8 minutes, 9 minutes or 10 minutes.In the present invention, the second stage preferably adjusts described
The pH value of the first condensation polymer is 5.0~5.1, can be specifically 5.0 or 5.1.In the present invention, the second stage and the 3rd
The interval time in stage is preferably 8~10 minutes, can be specifically 8 minutes, 9 minutes or 10 minutes.In the present invention, it is described
The pH value that phase III preferably adjusts first condensation polymer is 4.5~4.7, can be specifically 4.5,4.6 or 4.7.
In the present invention, the interval time of the phase III and fourth stage is controlled preferably through the viscosity of condensation polymer.This hair
It is bright preferably to enter fourth stage when the viscosity of first condensation polymer is for 16~16.5S (25 DEG C, apply 4# glasss), more preferably
16.1~16.4S, most preferably 16.2~16.3S.In the present invention, the fourth stage is above-mentioned regulation first polycondensation
The pH value of thing is 6~6.5, is no longer repeated herein.PH value of the present invention stage by stage to first condensation polymer is controlled
The reaction rate of formaldehyde and urea can be slowed down so that it is more abundant that the second polycondensation reaction is carried out.Substep adjustment pH of the invention
Value enables to gentle the carrying out of reaction, prevents reaction excessively fierce.Additionally it is possible to prevent product crystallisation solidification, cause anti-
Should be insufficient.
In the present invention, the temperature of second polycondensation reaction is preferably 90~95 DEG C, more preferably 91~94 DEG C, optimal
Elect 92~93 DEG C as；The time of second polycondensation reaction is preferably 20~40 minutes, more preferably 25~35 minutes, most preferably
It is 28~33 minutes.
After obtaining the second condensation polymer, the pH value of present invention regulation second condensation polymer for after 7.5~8, with remaining urea
Mixing carries out the 3rd polycondensation reaction, obtains the 3rd condensation polymer.Currently preferred the second condensation polymer to obtaining stands, when
The viscosity of second condensation polymer is that the pH value that 17~18S (25 DEG C, apply 4# glasss) adjusts second condensation polymer afterwards is 7.5~8,
More preferably 17.2~17.8S, most preferably 17.4~17.6S.The pH value of present invention regulation second condensation polymer for 7.5~
8, preferably 7.6~7.9, more preferably 7.7~7.8.The present invention is to adjusting the material of the second condensation polymer pH value without spy
It is different to require, using inorganic alkali lye well-known to those skilled in the art.In the present invention, inorganic alkali lye described herein with it is upper
State inorganic base liquid phase described in technical scheme same, no longer repeated herein.
In the present invention, the temperature of the 3rd polycondensation reaction is preferably 80~90 DEG C, more preferably 82~88 DEG C, optimal
Elect 84~86 DEG C as；The time of the 3rd polycondensation reaction is preferably 20~40 minutes, more preferably 25~35 minutes, most preferably
It is 28~33 minutes.
In the present invention, the mass ratio of first part of urea, second part of urea and remaining urea is preferably (50~60):
(20~25):(20~25), more preferably (52~58):(21~24):(21~24), most preferably (54~56):(22~
23):(22~23).
After obtaining the 3rd condensation polymer, the pH value of present invention regulation the 3rd condensation polymer is 7~7.5, obtains Lauxite
Adhesive.The pH value of present invention regulation the 3rd condensation polymer for 7~7.5, preferably 7.1~7.4, more preferably 7.2~
7.3.The present invention does not have particular/special requirement to the material for adjusting the 3rd condensation polymer pH value, using well known to those skilled in the art
Inorganic acid or organic acid.In the present invention, inorganic acid described herein and organic acid and nothing described in above-mentioned technical proposal
Machine acid is identical with organic acid, is no longer repeated herein.The pH value of present invention regulation the 3rd condensation polymer can for 7~7.5
Prevent adhesive from solidifying, produce blob of viscose, the viscosity and glue for improving adhesive such as use at the performance, additionally it is possible to extend
Storage time.
Made present invention also offers described in urea-formaldehyde resin adhesive described in a kind of above-mentioned technical proposal or above-mentioned technical proposal
The application of the urea-formaldehyde resin adhesive that Preparation Method is obtained, as the gluing of fiberboard, particieboard, woodwork plate and bamboo-wood plywood
Agent.
Urea-formaldehyde resin adhesive provided the present invention with reference to embodiment and its preparation method and application is carried out in detail
Explanation, but they can not be interpreted as limiting the scope of the present invention.
In embodiments of the present invention, unless otherwise specified, described part is mass parts.
Embodiment 1
Weigh the formalin that 139 parts of mass fractions are 37% once to add in reactor, and add 15 parts of water, adjust
Section pH value is 8.5, and 55.5 parts of purity of addition are 98% urea for the first time, are subsequently adding 3 parts of KH550 and 2 part of polyethylene glycol
(400) steam-stirring intensification, is opened.
Reactor is started to warm up from less than 50 DEG C, after heating up 40 minutes, temperature is raised to 90 DEG C, and is protected under 90 DEG C of states
Temperature reaction 30 minutes.After retention time arrives, remained under the conditions of 90 DEG C in temperature, first adjust pH value 5.8, adjusted again after spending 10 minutes
Section pH value 5.0, after adjusting pH value 4.7 after 8 minutes again.Tested viscosity, after viscosity reaches 16S (25 DEG C, apply 4# glasss), adjusts pH
After value 6.2, second addition, 21.5 parts of purity are 98% urea, and add 3 parts of Milled wood lignins, react 30 minutes, then survey
Viscosity, after viscosity reaches 17S (25 DEG C, apply 4# glasss), adjusts pH value 7.5.
After pH value 7.5 are adjusted, third time 23 parts of purity of addition are 98% urea, are incubated 20 minutes, and cooling down is arrived
40 DEG C, blowing after pH value 7.0 is adjusted, obtain urea-formaldehyde resin adhesive.
The urea-formaldehyde resin adhesive that will be obtained is used to produce medium density fibre board (MDF), and the product produced is according to national quality
Supervising and quarantining general bureau GB/T14732-2006《Timber industry adhesive ureaformaldehyde, phenolic aldehyde, melamine resin》、GB/
T17657-2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》、GB/T 18580-2008《House decorative material
Form aldehyde release limitation in wood-based plate and its product》And GB/T11718-2009《Medium density fibre board (MDF)》National standard detected,
Its performance test results is as shown in table 1.
The testing result of the urea-formaldehyde resin adhesive of table 1 and fiberboard (15mm plates) properties
As it can be seen from table 1 the content of free aldehyde in the urea-formaldehyde resin adhesive of the present embodiment is very low ,≤0.12%.It is raw
The MOR of the fiberboard of product is strong, internal bond strength and elastic modelling quantity are very high, is above standard figures；Thickness swelling rate
It is low with burst size of methanal, meet E0 grades of standard requirement.
Embodiment 2
Weigh the formaldehyde that 150 parts of mass fractions are 37% once to add in reactor, and add 5 parts of water, adjust pH value
It is 8.8,55.5 parts of purity of addition are 98% urea for the first time, are subsequently adding 2 parts of KH560 and 1.5 part of polyethylene glycol
(400) steam-stirring intensification, is opened.
Reactor is started to warm up from less than 50 DEG C, after heating up 45 minutes, temperature is raised to 95 DEG C, and is protected under 95 DEG C of states
Temperature reaction 30 minutes.After retention time arrives, remained under the conditions of 95 DEG C in temperature, first adjust pH value 6.0, adjusted again after spending 10 minutes
Section pH value 5.1, after adjusting pH value 4.5 after 10 minutes again.Tested viscosity, after viscosity reaches 16.5S (25 DEG C, apply 4# glasss), adjusts
After section pH value 6.5, second addition, 21.5 parts of purity are 98% urea, and add 3 parts of Corn cob lignins, react 30 points
Clock, then viscosimetric, after viscosity reaches 18S (25 DEG C, apply 4# glasss), adjust pH value 7.8.
After pH value 7.8 are adjusted, third time 23 parts of purity of addition are 98% urea, are incubated 20 minutes, and cooling down is arrived
40 DEG C, blowing after pH value 7.5 is adjusted, obtain urea-formaldehyde resin adhesive.
The urea-formaldehyde resin adhesive that will be obtained is used to produce particieboard, and the product produced supervises inspection according to national quality
Epidemic disease general bureau GB/T14732-2006《Timber industry adhesive ureaformaldehyde, phenolic aldehyde, melamine resin》、GB/T17657-
2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》、GB/T 18580-2008《House decorative material wood-based plate and
Form aldehyde release limitation in its product》And GB/T4897.3-2003《Particieboard》National standard detected, its performance test results
As shown in table 2.
The testing result of the urea-formaldehyde resin adhesive of table 2 and particieboard (15mm plates) properties
From table 2 it can be seen that the content of free aldehyde in the urea-formaldehyde resin adhesive of the present embodiment is very low ,≤0.15%.It is raw
The MOR of the particieboard of product is strong, internal bond strength and elastic modelling quantity are very high, is above standard figures；Thickness swelling rate
It is low with burst size of methanal, meet E0 grades of standard requirement.
Embodiment 3
Weigh the formaldehyde that 150 parts of mass fractions are 37% once to add in reactor, and add 10 parts of water, adjust pH value
8.6,55.5 parts of purity of addition are 98% urea for the first time, are subsequently adding 0.5 part of KH570 and 0.5 part of polyethylene glycol
(400) steam-stirring intensification, is opened.
Reactor is started to warm up from less than 50 DEG C, after heating up 45 minutes, temperature is raised to 93 DEG C, and is protected under 93 DEG C of states
Temperature reaction 30 minutes.After retention time arrives, remained under the conditions of 93 DEG C in temperature, first adjust pH value 6.0, adjusted again after spending 10 minutes
Section pH value 5.1, after adjusting pH value 4.5 after 10 minutes again.Tested viscosity, after viscosity reaches 16.5S (25 DEG C, apply 4# glasss), adjusts
After section pH value 6.5, second addition, 21.5 parts of purity are 98% urea, and add 0.5 part of straw lignin, react 30 points
Clock, then viscosimetric, after viscosity reaches 18S (25 DEG C, apply 4# glasss), adjust pH value 7.8.
After pH value 7.8 are adjusted, third time 23 parts of purity of addition are 98% urea, are incubated 30 minutes, and cooling down is arrived
40 DEG C, blowing after pH value 7.5 is adjusted, obtain urea-formaldehyde resin adhesive.
The urea-formaldehyde resin adhesive that will be obtained is used to produce core-board, and the product produced is supervised according to national quality
Quarantine general bureau GB/T14732-2006《Timber industry adhesive ureaformaldehyde, phenolic aldehyde, melamine resin》、GB/T17657-
2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》、GB/T 5849-2006《Core-board standard》、GB/T
18580-2008《Form aldehyde release limitation in house decorative material wood-based plate and its product》And the State Administration of Forestry《Forest system in 2015
Quality monitors sampling plan》Detected, its performance test results is as shown in table 3.
Table 3：The testing result of urea-formaldehyde resin adhesive and core-board properties
From table 3 it can be seen that the content of free aldehyde in the urea-formaldehyde resin adhesive of the present embodiment is very low ,≤0.15%.It is raw
The bending strength of the core-board of product, surface bonding intensity are very high, are above standard figures, and burst size of methanal is low, meets
E0 grades of standard requirement.
Embodiment 4
Weigh the formaldehyde that 152 parts of mass fractions are 37% once to add in reactor, and add 20 parts of water, adjust pH value
8.8,55.5 parts of purity of addition are 98% urea for the first time, are subsequently adding 1 part of DL602 and 1 part of polyethylene glycol (400), are opened
Steam-stirring heats up.
Reactor is started to warm up from less than 50 DEG C, after heating up 43 minutes, temperature is raised to 93 DEG C, and is protected under 93 DEG C of states
Temperature reaction 30 minutes.After retention time arrives, remained under the conditions of 93 DEG C in temperature, first adjust pH value 6.0, adjusted again after spending 10 minutes
Section pH value .1, after adjusting pH value 4.5 after 8 minutes again.Tested viscosity, after viscosity reaches 16.5S (25 DEG C, apply 4# glasss), regulation
After pH value 6.5, second addition, 21.5 parts of purity are 98% urea, and add 5 parts of bamboo matter lignin, react 30 minutes, then
Viscosimetric, after viscosity reaches 18S (25 DEG C, apply 4# glasss), adjusts pH value 7.5.
After pH value 7.5 are adjusted, third time 23 parts of purity of addition are 98% urea, are incubated 25 minutes, and cooling down is arrived
40 DEG C, blowing after pH value 7.0 is adjusted, obtain urea-formaldehyde resin adhesive.
The urea-formaldehyde resin adhesive that will be obtained is used to produce bamboo and wood glued board, and the product produced is according to national quality
Supervising and quarantining general bureau GB/T14732-2006《Timber industry adhesive ureaformaldehyde, phenolic aldehyde, melamine resin》、
GBT17657-2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》、GB/T 9846.1-GB/T 9846.12-
2004《National Standards for Plywood》With GB/T 18580-2008《Form aldehyde release limit in house decorative material wood-based plate and its product
Amount》Detected, its performance test results is as shown in table 4.
Table 4：The testing result of urea-formaldehyde resin adhesive and bamboo and wood glued board properties
From table 4, it can be seen that the content of free aldehyde in the urea-formaldehyde resin adhesive of the present embodiment is very low ,≤0.13%.It is raw
The bamboo and wood glued board burst size of methanal of product is low, meets E0 grades of standard requirement.
As seen from the above embodiment, the invention provides a kind of urea-formaldehyde resin adhesive, by comprising following mass fraction
Raw material is prepared：100 parts of urea, 50~60 parts of formaldehyde, 5~20 parts of water, 0.5~3 part of coupling agent, 0.5~2 part of polyethylene glycol
With 0.5~5 part of lignin.The urea-formaldehyde resin adhesive that the present invention is provided ensure that while burst size of methanal is reduced and be glued
Tie the mechanical property of product.It can be seen from experimental result according to embodiment, the urea-formaldehyde resin adhesive that the present invention is provided is creamy white,
The content of free aldehyde is less than 0.12%, and solid content is 41~58%, and viscosity is 17~30S.Additionally, the ureaformaldehyde tree that the present invention is provided
The MOR of sheet material prepared by fat adhesive is 20.1~28.9MPa, and elastic modelling quantity is 1689~2635MPa, and interior combination is strong
It is 0.39~0.58MPa to spend, and thickness swelling rate is 5.1~9.5%, and burst size of methanal is 0.11~0.42mg/L.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of urea-formaldehyde resin adhesive, is prepared by the raw material comprising following mass fraction：
2. urea-formaldehyde resin adhesive according to claim 1, it is characterised in that the lignin is Milled wood lignin, jade
One or more in rice core lignin, bamboo matter lignin and straw lignin.
3. urea-formaldehyde resin adhesive according to claim 1, it is characterised in that the coupling agent be polyisocyanates and/
Or organo-silicon coupling agent.
4. according to claims 1 to 3 any one urea-formaldehyde resin adhesive preparation method, comprise the following steps：
The first polycondensation reaction is carried out after formaldehyde, water, first part of urea, coupling agent and polyethylene glycol are mixed, the first polycondensation is obtained
Thing；
To carry out the second polycondensation anti-after 6~6.5, to mix with second part of urea and lignin to adjust the pH value of first condensation polymer
Should, obtain the second condensation polymer；
The pH value of second condensation polymer is adjusted after 7.5~8, the polycondensation reaction of row the 3rd to be mixed into remaining urea, the is obtained
Three condensation polymers；
It is 7~7.5 to adjust the pH value of the 3rd condensation polymer, obtains urea-formaldehyde resin adhesive.
5. preparation method according to claim 4, it is characterised in that the temperature of first polycondensation reaction is 90~95
℃；
The time of first polycondensation reaction is 20~40 minutes.
6. preparation method according to claim 4, it is characterised in that the temperature of second polycondensation reaction is 90~95
℃；
The time of second polycondensation reaction is 20~40 minutes.
7. preparation method according to claim 4, it is characterised in that the temperature of the 3rd polycondensation reaction is 80~90
℃；
The time of the 3rd polycondensation reaction is 20~40 minutes.
8. the preparation method according to claim 4~7 any one, it is characterised in that first part of urea, second part
The mass ratio of urea and remaining urea is (50~60):(20~25):(20~25).
9. urea-formaldehyde resin adhesive described in claims 1 to 3 any one or preparation side described in claim 4~8 any one
The application of the urea-formaldehyde resin adhesive that method is obtained, it is characterised in that as fiberboard, particieboard, woodwork plate and bamboo-wood plywood
Adhesive.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619650A (en) * | 2017-10-04 | 2018-01-23 | 镇江市星耀智能装备有限公司 | A kind of adhesive for water resistant sheet material |
| CN117511314A (en) * | 2023-10-26 | 2024-02-06 | 广州福诚美化工有限公司 | High-glossiness water-based paint and preparation process thereof |
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| CN1069509A (en) * | 1991-08-15 | 1993-03-03 | 鞠纯衡 | Lignin modified uric-aldehyde resin and production method thereof |
| CN103725233A (en) * | 2013-11-26 | 2014-04-16 | 沃太能源南通有限公司 | Preparation method of lignin-based urea-formaldehyde resin adhesive with low formaldehyde release |
| WO2014159661A1 (en) * | 2013-03-14 | 2014-10-02 | Georgia-Pacific Chemicals Llc | Urea mixtures and methods for making and using same |
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| WO2014159661A1 (en) * | 2013-03-14 | 2014-10-02 | Georgia-Pacific Chemicals Llc | Urea mixtures and methods for making and using same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107619650A (en) * | 2017-10-04 | 2018-01-23 | 镇江市星耀智能装备有限公司 | A kind of adhesive for water resistant sheet material |
| CN117511314A (en) * | 2023-10-26 | 2024-02-06 | 广州福诚美化工有限公司 | High-glossiness water-based paint and preparation process thereof |
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| CN106753104B (en) | 2020-05-05 |
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