CN109504325A - A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof - Google Patents
A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109504325A CN109504325A CN201811527645.5A CN201811527645A CN109504325A CN 109504325 A CN109504325 A CN 109504325A CN 201811527645 A CN201811527645 A CN 201811527645A CN 109504325 A CN109504325 A CN 109504325A
- Authority
- CN
- China
- Prior art keywords
- parts
- urea
- formaldehyde resin
- resin adhesive
- ageing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof, is specifically related to field of adhesive technology.The present invention includes the raw material of following weight part ratio: 944-1334 parts of formalin, 1100-1300 parts of urea, 423-503 parts of pyrimidines, 230-360 parts of tromethamine, 130-220 parts of age resister, 7-26 parts of sodium hydroxide and 9-31 parts of formic acid；Wherein, age resister are as follows: 60-80 parts of resveratrol, 53-67 parts of dehydrated alcohol, 45-61 parts of zein, 32-44 parts of montmorillonite powder and 15-22 parts of niacinamide.Ageing-resistant urea-formaldehyde resin adhesive environmental-protecting performance of the invention is high, and Storage period is long, can water-fast, high temperature resistant, for being able to extend the service life of wood-based plate after wood-based plate.Preparation method technique of the present invention is controllable, it is easily operated, be suitable for large-scale production.
Description
[technical field]
The present invention relates to field of adhesive technology, and in particular to a kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof.
[background technique]
In Wood-based Panel Production manufacturing process, adhesive is essential main component.With the increasing of adhesive usage amount
Add, requirement of the industry of artificial boards according to the difference of product to adhesive Optical instrument is different.In current industry of artificial boards
In, use scope it is most wide still be formaldehydes adhesive (urea-formaldehyde resin adhesive, phenolic resin glue, melamine-formaldehyde resin adhesive
Deng), it the advantage is that at low cost and preparation is convenient.In formaldehydes adhesive, the usage amount of urea-formaldehyde resin adhesive is maximum, oneself is through accounting for
According to the 90% of adhesion agent for artificial board, account for about 60% or more of entire wood working industry adhesive.With phenolic resin glue, trimerization
The adhesion agent for artificial board such as cyanamide formaldehyde resin adhesive are compared, and urea-formaldehyde resin adhesive is at low cost, curing rate is fast, processing performance
Advantages such as good, easy to operate, but there is also burst size of methanal height, water-fast, heat resistance is low disadvantage is water-fast low with heat resistance to lead
It causes to be easy to appear in use process and come unglued and aging, so that service life is shorter than another two classes adhesive, burst size of methanal is but higher than
Another two classes adhesive.
As country economizes on resources, to ureaformaldehyde to energy-saving and environment-friendly further attention for the service life for extending wood-based plate
The research of resin glue performance improvement just deepens continuously.Chinese invention patent Authorization Notice No. is CN103709350B, entitled gluing
A kind of use is disclosed in wood melamine-urea-formaldehyde resin and its patent document of preparation process and application method to add
Enter melamine and increase that urea-formaldehyde resin adhesive is water-fast, method of heat resistance, but its mid-early stage urea and formaldehyde addition reaction, can generate
Four kinds of different methylolurea products, product diversity will affect the degree of cross linking of melamine polycondensation reaction, to influence gluing
Agent quality, it is water-fast when adhesive being caused to produce in batches and heat resistance unstable.Chinese patent Authorization Notice No. is
In the patent document of CN103804619B, entitled lignin-phenol-urea-formaldehyde condensation copolymerization resin adhesive and preparation method
It also discloses and a kind of water-fast, environmentally friendly condensation copolymerization resin adhesive is obtained using lignin, phenol, urea and formaldehyde condensation copolymerization
Method, but lignin be aroma type high polymer, phenyl ring distributed quantity is intensive, causes adhesive brittleness big, easy fracture.
In conclusion also meet urgent need of the common people to green living for the call of response national energy-saving environmental protection, it is anxious
A kind of environmentally friendly, water-fast, heat-resisting ageing-resistant urea-formaldehyde resin adhesive need to be developed in the production of wood-based plate.
[summary of the invention]
Goal of the invention of the invention is, water-fast for urea-formaldehyde resin adhesive, heat resistance is low, the high problem of burst size of methanal,
A kind of ageing-resistant urea-formaldehyde resin adhesive is provided.Ageing-resistant urea-formaldehyde resin adhesive environmental-protecting performance of the invention is high, and Storage period is long, can be resistant to
Water, high temperature resistant, for being able to extend the service life of wood-based plate after wood-based plate.Preparation method technique of the present invention is controllable, is easy to grasp
Make, be suitable for large-scale production.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 944-1334 parts of formalin, urea
1100-1300 parts, 423-503 parts of pyrimidines, 230-360 parts of tromethamine, 130-220 parts of age resister, hydroxide
7-26 parts and formic acid 9-31 parts of sodium；The age resister includes the raw material of following weight part ratio: 60-80 parts of resveratrol, anhydrous
53-67 parts of ethyl alcohol, 45-61 parts of zein, 32-44 parts of montmorillonite powder and 15-22 parts of niacinamide.
Optimization, the age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, then take
Niacinamide, white reed alcohol, first part of montmorillonite powder and dehydrated alcohol are added in reaction kettle, are then warming up to 120-144 DEG C, are protected
Temperature reaction 200-220 minutes, is then cooled to 80-90 DEG C, and zein is added, and stirs 8-16 minutes, and it is de- to add second part of illiteracy
Mountain flour stirs 10-18 minutes, then dries at 74-86 DEG C to no alcohol taste, obtain age resister.
It advanced optimizes, the weight part ratio of first part of montmorillonite powder and second part of montmorillonite powder is 1:50-60.
Further optimize, the pyrimidines are in uracil, 5-hydroxylmethyluracil and thymidine
Any one.
Further optimize again, the mass percent concentration of the formalin is 33%-36%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, tromethamine is divided into two parts；
B. it takes formalin and pyrimidines to be added in reaction kettle, adjusts pH value to 8.1-8.4 with sodium hydroxide,
Then heat to 71-76 DEG C, insulation reaction 25-33 minutes；
C. first part of urea is added, is kept for 71-76 DEG C reaction 45-55 minutes, then with first acid for adjusting pH to 5.2-5.6
Afterwards, it is warming up to 84-90 DEG C, insulation reaction 85-105 minutes；
D. it is cooled to 75-78 DEG C, then second part of urea of addition and first part of tromethamine, insulation reaction 30-45 minutes；
E. pH to 8.6-8.9 is adjusted with sodium hydroxide, then heats to 94-100 DEG C, adds second part of tromethamine,
Insulation reaction 34-42 minutes；
F. be added age resister, kept for 50-60 DEG C stirring 10-18 minutes, be then cooled to 32-42 DEG C, can plastic emitting, obtain
Ageing-resistant urea-formaldehyde resin adhesive；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 30-40 DEG C of holding vessel, is saved backup.
Optimization, the weight part ratio of first part of urea and second part of urea is 3-7:1.
It advanced optimizes, the weight part ratio of first part of tromethamine and second part of tromethamine is 2-5:1.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the present invention is first reacted using formaldehyde with pyrimidines, then urea and tromethamine are added in two portions respectively,
It is eventually adding the preparation method of age resister, the degree of cross linking of urea-formaldehyde resin adhesive is effectively reduced, enhances stability, extends shelf life,
And pyrimidine ring and tromethamine chain structure are introduced in urea-formaldehyde resin adhesive system, so that adhesive is kept high bonding strength,
To realize enhanced water resistance and high-fire resistance, while the usage amount of formaldehyde can be substantially reduced again, be reduced to formaldehyde, urea mol ratio
0.9 or less.Preparation method technique of the present invention is controllable, it is easily operated, be suitable for large-scale production.
2. the present invention prepares Lauxite, by the way that pyrimidines, tromethamine and age resister is added, urea is improved
The feature of environmental protection and stability of urea formaldehyde glue, so that the shelf life extends to 40 days or more, meanwhile, water resistance and heat resistance also obtain
It improves, so that the bonding strength of wood-based plate reaches 1.8MPa or more.The addition of pyrimidines and tromethamine, PARA FORMALDEHYDE PRILLS(91,95) play
Solidification also plays sealing process to active group, thus greatly reduces the molar ratio of formaldehyde, urea, improves gluing
The environmental-protecting performance of agent is able to maintain burst size of methanal, hereinafter, even if in damp and hot destructive testing, also down to 0.31mg/L
0.37mg/L is hereinafter, show also reach good water-fast heat resistance in the use process for wood-based plate.
Firstly, formaldehyde first reacted with pyrimidines, then with first part of urea reaction, it is possible to reduce free formaldehyde content
With figure molecule generation quantity, and the reduction of figure molecular amounts can increase the stability and bonding strength of adhesive, effectively
Extend the storage time of adhesive.Formaldehyde and pyrimidines addition reaction generate the hydroxymethyl derivative with pyrimidine ring, ring
Shape structure can cause certain steric hindrance to methylol thereon, make the reduction of methylol activity, avoid intermolecular into one
Step crosslinking, thus make be added first part of urea preferentially first reacted with unreacted formaldehyde, generate methylolurea, then again with it is phonetic
Methylol reaction in phenazine ring, is conducive to generate linear polymer and noncrosslinking figure molecule.Wherein, first in alkaline condition
Under, it reacts first part of urea being added preferentially with formaldehyde, can just set about reducing free first from the initial stage of preparation process
The content of aldehyde, then in acid condition, activate the methylol on pyrimidine ring, methylol thereon is made to participate in form linear polymerization
In the reaction of object, and further formaldehyde is fixed in the molecular structure of adhesive by chemical bond, is prevented under hygrothermal environment
Adhesive degradation dissociates formaldehyde again, provides the heat resistance of adhesive.
Secondly, continuously adding second part of urea and first part of tromethamine, urea can be made to continue to participate in reaction, towards formation
The direction of linear polymer carries out, and by introducing tromethamine, closes excessive methylol active group and imino group activity
Group controls the crosslinking degree of polymer, carries out polycondensation reaction orderly, leniently, reduces the quantity for generating figure molecule, protects
Card forms stable linear polymer, extends the storage time of adhesive, and due to the reduction of methylol and imino group, make gluing
The hydrophobicity of agent enhances, and also improves water resistance.
And then second part of tromethamine is added, under the action of alkalinity and heating, the reaction of polycondensation reaction can be reduced
Rate, and the speed for closing unreacted active group is improved, the water resistance of adhesive is further increased, adhesive is also prevented from and exists
Because there is crosslinking hardening during storage, and stability and bonding strength decline, meanwhile, and the trip for having neither part nor lot in reaction can be combined
From formaldehyde, this part formaldehyde is fixed in linear polymer by chemical bond, prevents formaldehyde from being dissociateed easily and come.
Finally, joined age resister, adhesive can be made not occur being excessively crosslinked and solidifying during storage, extended
In the shelf life, also can make adhesive in use has significant heat resistance and water resistance, prolongs the service life.Wherein,
Using ethyl alcohol as solvent, niacinamide and resveratrol under the catalysis of montmorillonite powder, dehydration polymerization at contain numerous phenyl ring and pyridine
The high molecular polymer of ring structure, is then added zein, covers one layer of fire resistant water resistant albumen shape on polymer molecule surface
Consolidate at support, adds montmorillonite powder, mixed, using the metal ion in montmorillonite powder structure sheaf, make age resister
Generate electronegativity.High score after age resister is added in adhesive, under the dual dynamic of heating and stirring, in age resister
Sub- polymer is attached to adhesive molecular surface, forms the fine and close heat-resisting waterproof membrane of macromolecule, protects under adhesive hot environment
Structure is not destroyed, and chance is wet not to be permeated by hydrone, improves the heat resistance and water resistance of adhesive, while age resister
Montmorillonite powder in metal ion electropositive, and adhesive molecule is made to become positively charged, generates mutually exclusive, generation can not be assembled
Crosslinking curing extends storage stability and storage time.Montmorillonite powder plays the role of two kinds, and first part of montmorillonite powder plays catalysis
Effect, dosage is few, and second part of montmorillonite powder plays anti-solidification, and dosage is more.
Urea is added in preparation process of the present invention by several times, the additional amount of strict control urea, being capable of forming reaction has
Stablize the linear molecule of the degree of cross linking, and using tromethamine is added by several times and controls the additional amount of tromethamine, control closing is lived
Property group speed and quantity, to obtain stability high, water resistance and heat-resist adhesive.
3. the pyrimidine ring in invention adhesive structure has double alcohol of formula and diketone formula interconversion, cyclic structure is enable to generate one
Determine the deformation of degree, so that the adhesive made has flexibility, it is not easy to break, stability is improved, so that extending makes
Use the service life.For the present invention by a large amount of creative experimental studies, verifying obtains selection uracil, 5-hydroxylmethyluracil and thymus gland
These three pyrimidines of pyrimidine can preferably generate the methylol of low activity with formaldehyde, be conducive to adhesive and form line style
Molecule, and other pyrimidines such as cytimidine, pyrimidine are used, the methylol activity formed with formaldehyde is high, produces adhesive
Raw crosslinking curing, stability and ageing resistance are deteriorated.
[specific embodiment]
Below with reference to embodiment, the invention will be further described.
Embodiment 1
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 944 parts of formalin, 1100 parts of urea,
423 parts of uracil, 230 parts of tromethamine, 130 parts of age resister, 7 parts of sodium hydroxide and 9 parts of formic acid；Age resister includes following
The raw material of weight part ratio: 60 parts of resveratrol, 53 parts of dehydrated alcohol, 45 parts of zein, 32 parts of montmorillonite powder and 15 parts of niacinamide.
Wherein, age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, first part of montmorillonite
The weight part ratio of powder and second part of montmorillonite powder is 1:50, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 120 DEG C, insulation reaction 200 minutes, is then cooled to 80 DEG C, zein is added,
Stirring 8 minutes adds second part of montmorillonite powder, stirs 10 minutes, then dries at 74 DEG C to no alcohol taste, obtain anti-aging
Agent.
The mass percent concentration of formalin is 33%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, the weight part ratio of first part of urea and second part of urea is 3:1, will
Tromethamine is divided into two parts, and the weight part ratio of first part of tromethamine and second part of tromethamine is 2:1；
B. it takes formalin and uracil to be added in reaction kettle, adjusts pH value to 8.1 with sodium hydroxide, then heat to
71 DEG C, insulation reaction 25 minutes；
C. first part of urea is added, is kept for 71 DEG C react 45 minutes, then with after first acid for adjusting pH to 5.2, is warming up to 84
DEG C, insulation reaction 85 minutes；
D. 75 DEG C are cooled to, then second part of urea of addition and first part of tromethamine, insulation reaction 30 minutes；
E. pH to 8.6 is adjusted with sodium hydroxide, then heats to 94 DEG C, adds second part of tromethamine, insulation reaction
34 minutes；
F. age resister is added, keep 50 DEG C stir 10 minutes, be then cooled to 32 DEG C, can plastic emitting, obtain ageing-resistant urea
Urea formaldehyde glue；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 30 DEG C of holding vessel, is saved backup.
Embodiment 2
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 1334 parts of formalin, urea 1300
Part, 503 parts of thymidine, 360 parts of tromethamine, 220 parts of age resister, 26 parts of sodium hydroxide and 31 parts of formic acid；Age resister
Raw material including following weight part ratio: 80 parts of resveratrol, 67 parts of dehydrated alcohol, 61 parts of zein, 44 parts of montmorillonite powder and cigarette
22 parts of amide.
Wherein, age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, first part of montmorillonite
The weight part ratio of powder and second part of montmorillonite powder is 1:60, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 144 DEG C, insulation reaction 220 minutes, is then cooled to 90 DEG C, zein is added,
Stirring 16 minutes adds second part of montmorillonite powder, stirs 18 minutes, then dries at 86 DEG C to no alcohol taste, obtain anti-aging
Agent.
The mass percent concentration of formalin is 36%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, the weight part ratio of first part of urea and second part of urea is 7:1, will
Tromethamine is divided into two parts, and the weight part ratio of first part of tromethamine and second part of tromethamine is 5:1；
B. it takes formalin and thymidine to be added in reaction kettle, adjusts pH value to 8.4 with sodium hydroxide, then heat up
To 76 DEG C, insulation reaction 33 minutes；
C. first part of urea is added, is kept for 76 DEG C react 55 minutes, then with after first acid for adjusting pH to 5.6, is warming up to 90
DEG C, insulation reaction 105 minutes；
D. 78 DEG C are cooled to, then second part of urea of addition and first part of tromethamine, insulation reaction 45 minutes；
E. pH to 8.9 is adjusted with sodium hydroxide, then heats to 100 DEG C, adds second part of tromethamine, insulation reaction
42 minutes；
F. age resister is added, keep 60 DEG C stir 18 minutes, be then cooled to 42 DEG C, can plastic emitting, obtain ageing-resistant urea
Urea formaldehyde glue；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 40 DEG C of holding vessel, is saved backup.
Embodiment 3
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 1040 parts of formalin, urea 1150
Part, 443 parts of 5-hydroxylmethyluracil, 265 parts of tromethamine, 150 parts of age resister, 12 parts of sodium hydroxide and 14.5 parts of formic acid；
Age resister includes the raw material of following weight part ratio: 65 parts of resveratrol, 57 parts of dehydrated alcohol, 49 parts of zein, montmorillonite powder
35 parts and 17 parts of niacinamide.
Wherein, age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, first part of montmorillonite
The weight part ratio of powder and second part of montmorillonite powder is 1:53, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 126 DEG C, insulation reaction 205 minutes, is then cooled to 82 DEG C, zein is added,
Stirring 10 minutes adds second part of montmorillonite powder, stirs 12 minutes, then dries at 77 DEG C to no alcohol taste, obtain anti-aging
Agent.
The mass percent concentration of formalin is 34%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, the weight part ratio of first part of urea and second part of urea is 4:1, will
Tromethamine is divided into two parts, and the weight part ratio of first part of tromethamine and second part of tromethamine is 3:1；
B. it takes formalin and 5-hydroxylmethyluracil to be added in reaction kettle, adjusts pH value to 8.2, so with sodium hydroxide
After be warming up to 72 DEG C, insulation reaction 27 minutes；
C. first part of urea is added, is kept for 72 DEG C react 47 minutes, then with after first acid for adjusting pH to 5.3, is warming up to 85
DEG C, insulation reaction 90 minutes；
D. 76 DEG C are cooled to, then second part of urea of addition and first part of tromethamine, insulation reaction 33 minutes；
E. pH to 8.7 is adjusted with sodium hydroxide, then heats to 95 DEG C, adds second part of tromethamine, insulation reaction
36 minutes；
F. age resister is added, keep 53 DEG C stir 12 minutes, be then cooled to 35 DEG C, can plastic emitting, obtain ageing-resistant urea
Urea formaldehyde glue；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 32 DEG C of holding vessel, is saved backup.
Embodiment 4
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 1240 parts of formalin, urea 1250
Part, 483 parts of 5-hydroxylmethyluracil, 327 parts of tromethamine, 200 parts of age resister, 21 parts of sodium hydroxide and 25.5 parts of formic acid；
Age resister includes the raw material of following weight part ratio: 75 parts of resveratrol, 63 parts of dehydrated alcohol, 57 parts of zein, montmorillonite powder
41 parts and 20 parts of niacinamide.
Wherein, age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, first part of montmorillonite
The weight part ratio of powder and second part of montmorillonite powder is 1:58, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 138 DEG C, insulation reaction 215 minutes, is then cooled to 88 DEG C, zein is added,
Stirring 14 minutes adds second part of montmorillonite powder, stirs 16 minutes, then dries at 83 DEG C to no alcohol taste, obtain anti-aging
Agent.
The mass percent concentration of formalin is 35%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, the weight part ratio of first part of urea and second part of urea is 6:1, will
Tromethamine is divided into two parts, and the weight part ratio of first part of tromethamine and second part of tromethamine is 4.5:1；
B. it takes formalin and 5-hydroxylmethyluracil to be added in reaction kettle, adjusts pH value to 8.3, so with sodium hydroxide
After be warming up to 75 DEG C, insulation reaction 31 minutes；
C. first part of urea is added, is kept for 75 DEG C react 52 minutes, then with after first acid for adjusting pH to 5.5, is warming up to 89
DEG C, insulation reaction 100 minutes；
D. 77 DEG C are cooled to, then second part of urea of addition and first part of tromethamine, insulation reaction 41 minutes；
E. pH to 8.8 is adjusted with sodium hydroxide, then heats to 98 DEG C, adds second part of tromethamine, insulation reaction
40 minutes；
F. age resister is added, keep 57 DEG C stir 16 minutes, be then cooled to 40 DEG C, can plastic emitting, obtain ageing-resistant urea
Urea formaldehyde glue；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 38 DEG C of holding vessel, is saved backup.
Embodiment 5
A kind of ageing-resistant urea-formaldehyde resin adhesive, the raw material including following weight part ratio: 1140 parts of formalin, urea 1200
Part, 463 parts of 5-hydroxylmethyluracil, 295 parts of tromethamine, 175 parts of age resister, 16.5 parts of sodium hydroxide and 20 parts of formic acid；
Age resister includes the raw material of following weight part ratio: 70 parts of resveratrol, 60 parts of dehydrated alcohol, 53 parts of zein, montmorillonite powder
38 parts and 18.5 parts of niacinamide.
Wherein, age resister the preparation method comprises the following steps: by weight, montmorillonite powder is divided into two parts, first part of montmorillonite
The weight part ratio of powder and second part of montmorillonite powder is 1:55, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 132 DEG C, insulation reaction 210 minutes, is then cooled to 85 DEG C, zein is added,
Stirring 12 minutes adds second part of montmorillonite powder, stirs 14 minutes, then dries at 80 DEG C to no alcohol taste, obtain anti-aging
Agent.
The mass percent concentration of formalin is 35%.
A kind of preparation method of above-mentioned ageing-resistant urea-formaldehyde resin adhesive, comprising the following steps:
A. by weight, urea is divided into two parts, the weight part ratio of first part of urea and second part of urea is 5:1, will
Tromethamine is divided into two parts, and the weight part ratio of first part of tromethamine and second part of tromethamine is 3.5:1；
B. it takes formalin and 5-hydroxylmethyluracil to be added in reaction kettle, adjusts pH value to 8.2, so with sodium hydroxide
After be warming up to 73 DEG C, insulation reaction 29 minutes；
C. first part of urea is added, is kept for 73 DEG C react 50 minutes, then with after first acid for adjusting pH to 5.4, is warming up to 87
DEG C, insulation reaction 95 minutes；
D. 76 DEG C are cooled to, then second part of urea of addition and first part of tromethamine, insulation reaction 37 minutes；
E. pH to 8.8 is adjusted with sodium hydroxide, then heats to 97 DEG C, adds second part of tromethamine, insulation reaction
38 minutes；
F. age resister is added, keep 55 DEG C stir 14 minutes, be then cooled to 37 DEG C, can plastic emitting, obtain ageing-resistant urea
Urea formaldehyde glue；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 35 DEG C of holding vessel, is saved backup.
Embodiment 6
Difference with embodiment 5 is, replaces 5-hydroxylmethyluracil with pyrimidine, remaining step is identical.
Embodiment 7
Difference with embodiment 5 is, replaces 5-hydroxylmethyluracil with cytimidine, remaining step is identical.
Embodiment 8
Difference with embodiment 5 is, the operation that 5-hydroxylmethyluracil reaction is added, remaining step are omitted in step a
It is identical.
Embodiment 9
Difference with embodiment 5 is, will be advanced to first part of addition with the operation of first acid for adjusting pH to 5.4 in step c
It is carried out after urea, remaining step is identical.
Embodiment 10
Difference with embodiment 5 is, the operation that first acid for adjusting pH is added is omitted in step c, remaining step is identical.
Embodiment 11
Difference with embodiment 5 is, the operation that the reaction of second part of tromethamine is added, remaining step are omitted in step e
It is identical.
Embodiment 12
Difference with embodiment 5 is, is added without age resister in step f, remaining step is identical.
Embodiment 13
Difference with embodiment 5 is, first part of montmorillonite powder is added without when preparing age resister, remaining step is identical.
Embodiment 14
Difference with embodiment 5 is, second part of montmorillonite powder is added without when preparing age resister, remaining step is identical.
Embodiment 15
Difference with embodiment 5 is, is added without zein when preparing age resister, remaining step is identical.
The comparison of 16 implementation result of embodiment
1. the preparation of laboratory sample
Selection is prepared by the method for embodiment 1-15 with a collection of raw material, obtains laboratory sample 1-15.
2. evaluation method
2.1. the viscosity, Storage period of measurement experiment sample 1-15, and use laboratory sample 1-15 routinely gluing and hot pressing
Technique (glue-spread 120/m2, single spreading, pressure 1MPa, 120 DEG C of temperature, time 5min) and compacting veneer, wood-based plate is obtained, is surveyed
The bonding strength and burst size of methanal of fixed each wood-based plate.Detailed results are shown in Table 1.
2.2. the laboratory sample 1-15 wood-based plate prepared is placed under hygrothermal environment and carries out failure test, simulate use process
In extreme environment, respectively at the 0th day, the 7th day, the 14th day sampling and measuring bonding strength and burst size of methanal, investigation was used
The water-fast of urea-formaldehyde resin adhesive, high temperature resistant and environmental-protecting performance in journey, wherein the temperature of hygrothermal environment is 60 ± 2 DEG C, relative humidity is
90% ± 5%.Detailed results are shown in Table 2.
3. evaluation result
1 urea-formaldehyde resin adhesive performance measurement result of table
The wood-based plate wet-hot aging performance measurement result of 2 urea-formaldehyde resin adhesive of table preparation
4. experimental result
As seen from Table 1, the Storage period of laboratory sample 1-5 is longer than laboratory sample 6-14, and the bonding strength of laboratory sample 1-5 is real
Sample 6-11 is tested, the burst size of methanal of laboratory sample 1-5 is lower than laboratory sample 6-11.From table 2 it can be seen that laboratory sample 1-5
The water-fast of the wood-based plate of preparation, high temperature resistance are better than the wood-based plate of laboratory sample 6-14 preparation, show as under hygrothermal environment
In 14 days of storage, the wood-based plate bonding strength and burst size of methanal of laboratory sample 1-5 preparation are held in maintenance level, do not go out
Existing significant change, and the bonding strength of the wood-based plate of laboratory sample 6-14 preparation is decreased obviously, and burst size of methanal occurs
It is significantly raised.
5-hydroxylmethyluracil is replaced with pyrimidine in laboratory sample 6, replaces 5- methylol to urinate with cytimidine in laboratory sample 7
Pyrimidine is added without 5-hydroxylmethyluracil in laboratory sample 8, and the quantity for making reaction generate linear molecule is reduced, and figure
Molecular amounts increase, and Lauxite adhesiveness is caused to increase, and Storage period shortens, and bonding strength reduces, and burst size of methanal increases；?
In damp and hot failure test, urea-formaldehyde resin adhesive bonding strength is constantly reduced, and burst size of methanal constantly increases, and shows water-fast and high temperature resistant
Performance is decreased obviously.
First part of urea being added in laboratory sample 9 participates in reaction in acid condition always, so that reaction generates line style
The quantity of molecule is reduced, and figure molecular amounts increase, and Lauxite adhesiveness is caused to increase, and Storage period shortens, bonding strength
It reduces, burst size of methanal increases；In damp and hot failure test, urea-formaldehyde resin adhesive bonding strength is constantly reduced, and burst size of methanal is not
It is disconnected to increase, show that water-fast and high temperature resistance is decreased obviously.
First part of urea being added in laboratory sample 10 participates in reaction under alkaline condition always, so that linear molecule generates
Quantity is reduced, and formaldehyde is fixed not exclusively, and Lauxite adhesiveness is caused to increase, and Storage period shortens, and bonding strength reduces, and formaldehyde is released
High-volume increase；In damp and hot failure test, urea-formaldehyde resin adhesive bonding strength is constantly reduced, and burst size of methanal constantly increases, and is shown
Water-fast and high temperature resistance is decreased obviously.
Second part of tromethamine is added without in laboratory sample 11, so that active group and free formaldehyde residual, lead to ureaformaldehyde
Resin adhesiveness increases, and burst size of methanal increases, but also occur crosslinking hardening during storage quickly, bonding strength decline, storage
The phase of depositing shortens；Meanwhile in damp and hot failure test, urea-formaldehyde resin adhesive bonding strength is constantly reduced, and burst size of methanal constantly increases,
Show that water-fast and high temperature resistance is decreased obviously.
It is added without age resister in laboratory sample 12, when rigid preparation is completed, urea-formaldehyde resin adhesive performance does not have with laboratory sample 5
There is a difference, but due to the protection of not no age resister, so that its Storage period shortens, it is glued strong after damp and hot failure test
Degree constantly reduces, and burst size of methanal constantly increases, and shows that water-fast and high temperature resistance is decreased obviously.
In laboratory sample 13 when preparing age resister, it is added without first part of montmorillonite powder, when rigid preparation is completed, ureaformaldehyde
Resin glue performance and laboratory sample 5 do not have a difference, but due to the catalytic action of not no montmorillonite powder, so that age resister fails shape
At the heat-resisting water-fast polymeric membrane of stable structure, urea-formaldehyde resin adhesive Storage period is caused to shorten, after damp and hot failure test, glue
Closing intensity constantly reduces, and burst size of methanal constantly increases, and shows that water-fast and high temperature resistance is decreased obviously.
In laboratory sample 14 when preparing age resister, it is added without second part of montmorillonite powder, when rigid preparation is completed, ureaformaldehyde
Resin glue performance has essentially no difference with laboratory sample 5, but due to the electronegativity effect of not no montmorillonite powder, so that in reaction point
Son is assembled, and generates crosslinking curing, urea-formaldehyde resin adhesive Storage period is caused to shorten, glued strong after damp and hot failure test
Degree constantly reduces, and burst size of methanal constantly increases, and shows that water-fast and high temperature resistance is decreased obviously.
In laboratory sample 15 when preparing age resister, zein is not added, when rigid preparation is completed, performance and experiment sample
Product 5 have essentially no difference, but the support of the water-fast albumen of high temperature due to not having zein to be formed, so that the protectiveness of age resister
It can decline, cause urea-formaldehyde resin adhesive Storage period to shorten, after damp and hot failure test, bonding strength is constantly reduced, and formaldehyde is released
It high-volume constantly increases, shows that water-fast and high temperature resistance is decreased obviously.
Above description is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
Bright patent claim, it is all the present invention suggested by technical spirit under completed same changes or modifications change, should all belong to
In the covered the scope of the patents of the present invention.
Claims (8)
1. a kind of ageing-resistant urea-formaldehyde resin adhesive, which is characterized in that the raw material including following weight part ratio: formalin 944-1334
Part, 1100-1300 parts of urea, 423-503 parts of pyrimidines, 230-360 parts of tromethamine, 130-220 parts of age resister,
7-26 parts and formic acid 9-31 parts of sodium hydroxide；The age resister includes the raw material of following weight part ratio: resveratrol 60-80
Part, 53-67 parts of dehydrated alcohol, 45-61 parts of zein, 32-44 parts of montmorillonite powder and 15-22 parts of niacinamide.
2. a kind of ageing-resistant urea-formaldehyde resin adhesive according to claim 1, which is characterized in that the preparation side of the age resister
Method are as follows: by weight, montmorillonite powder is divided into two parts, then takes niacinamide, white reed alcohol, first part of montmorillonite powder and anhydrous
Ethyl alcohol is added in reaction kettle, is then warming up to 120-144 DEG C, insulation reaction 200-220 minutes, is then cooled to 80-90 DEG C,
Zein is added, stirs 8-16 minutes, adds second part of montmorillonite powder, stirs 10-18 minutes, is then done at 74-86 DEG C
It is dry to no alcohol taste, obtain age resister.
3. a kind of ageing-resistant urea-formaldehyde resin adhesive according to claim 2, which is characterized in that first part of montmorillonite powder with
The weight part ratio of second part of montmorillonite powder is 1:50-60.
4. a kind of ageing-resistant urea-formaldehyde resin adhesive according to claim 1, which is characterized in that the pyrimidines are urine
Any one in pyrimidine, 5-hydroxylmethyluracil and thymidine.
5. a kind of ageing-resistant urea-formaldehyde resin adhesive according to claim 1, which is characterized in that the quality hundred of the formalin
Dividing specific concentration is 33%-36%.
6. a kind of preparation method of ageing-resistant urea-formaldehyde resin adhesive of any of claims 1-5, which is characterized in that including
Following steps:
A. by weight, urea is divided into two parts, tromethamine is divided into two parts；
B. it takes formalin and pyrimidines to be added in reaction kettle, adjusts pH value to 8.1-8.4, then with sodium hydroxide
It is warming up to 71-76 DEG C, insulation reaction 25-33 minutes；
C. first part of urea is added, is kept for 71-76 DEG C reaction 45-55 minutes, then with after first acid for adjusting pH to 5.2-5.6, rises
Temperature is to 84-90 DEG C, insulation reaction 85-105 minutes；
D. it is cooled to 75-78 DEG C, then second part of urea of addition and first part of tromethamine, insulation reaction 30-45 minutes；
E. pH to 8.6-8.9 is adjusted with sodium hydroxide, then heats to 94-100 DEG C, adds second part of tromethamine, kept the temperature
Reaction 34-42 minutes；
F. be added age resister, kept for 50-60 DEG C stirring 10-18 minutes, be then cooled to 32-42 DEG C, can plastic emitting, obtain it is resistance to always
Change urea-formaldehyde resin adhesive；
G. ageing-resistant urea-formaldehyde resin adhesive is deposited in 30-40 DEG C of holding vessel, is saved backup.
7. a kind of preparation method of ageing-resistant urea-formaldehyde resin adhesive according to claim 6, which is characterized in that described first part
The weight part ratio of urea and second part of urea is 3-7:1.
8. a kind of preparation method of ageing-resistant urea-formaldehyde resin adhesive according to claim 6, which is characterized in that described first part
The weight part ratio of tromethamine and second part of tromethamine is 2-5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811527645.5A CN109504325A (en) | 2018-12-13 | 2018-12-13 | A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811527645.5A CN109504325A (en) | 2018-12-13 | 2018-12-13 | A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109504325A true CN109504325A (en) | 2019-03-22 |
Family
ID=65752529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811527645.5A Pending CN109504325A (en) | 2018-12-13 | 2018-12-13 | A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109504325A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834183A (en) * | 2006-03-07 | 2006-09-20 | 许盛英 | Urea resin additive |
| WO2009081988A1 (en) * | 2007-12-25 | 2009-07-02 | Bridgestone Corporation | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord, and method for producing rubber product |
| CN103497715A (en) * | 2013-08-28 | 2014-01-08 | 南京和木新材料科技发展有限公司 | Strong glue |
| 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 |
-
2018
- 2018-12-13 CN CN201811527645.5A patent/CN109504325A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834183A (en) * | 2006-03-07 | 2006-09-20 | 许盛英 | Urea resin additive |
| WO2009081988A1 (en) * | 2007-12-25 | 2009-07-02 | Bridgestone Corporation | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord, and method for producing rubber product |
| CN103497715A (en) * | 2013-08-28 | 2014-01-08 | 南京和木新材料科技发展有限公司 | Strong glue |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 余海帆: "脲醛树脂改性研究", 《中国优秀博硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王志晖等: "玉米朊的性质特征、生产现状与应用前景", 《粮食与食品工业》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Younesi-Kordkheili et al. | Improving urea formaldehyde resin properties by glyoxalated soda bagasse lignin | |
| RU2508192C2 (en) | Binder for bonding materials based on wood chips and/or wood fibres, method of its manufacture and corresponding moulding product | |
| CN101265314A (en) | Environmental protection urea-formaldehyde resin and preparation method thereof | |
| CN101549519B (en) | Manufacturing method of high-moisture-proof and high-density fiber board | |
| CN101511960A (en) | Novel hybrid binder with natural compounds for low emission products | |
| Liu et al. | Free formaldehyde reduction in urea-formaldehyde resin adhesive: Modifier addition effect and physicochemical property characterization | |
| CN104762045A (en) | Production method of modified urea resin adhesive | |
| CN1099328A (en) | Light shaving board and its producing process | |
| Gadhave et al. | Factor affecting gel time/process-ability of urea formaldehyde resin based wood adhesives | |
| CN101946034A (en) | Resin for producing an inorganic fiber material | |
| CN110684485B (en) | Environment-friendly adhesive with ultrahigh solid content for plywood, preparation method and application thereof | |
| CN103804619B (en) | Xylogen-phenol-urea-formaldehyde condensation copolymerization resin tackiness agent and preparation method | |
| Fan et al. | Curing characteristics of low molar ratio urea-formaldehyde resins | |
| CN106883800A (en) | A kind of Resin adhesive and preparation method thereof | |
| Pizzi | Urea and melamine aminoresin adhesives | |
| CN109504325A (en) | A kind of ageing-resistant urea-formaldehyde resin adhesive and preparation method thereof | |
| CN109439244A (en) | Sodium lignin sulfonate-melamine-formaldehyde copolymer resins wood adhesive and preparation method thereof | |
| CN103319674B (en) | Preparation method for natural vegetable gum-modified urea-formaldehyde resin | |
| CN1616510A (en) | Production of modified dimeric cyanamide urea formadehyde copolymer resin and its use for producing dipped paper | |
| CN105754546B (en) | A kind of dregs of beans lignin-base adhesive and preparation method thereof | |
| AU2007266778B2 (en) | Aminoplast resin of high performance for lignocellulosic materials | |
| CN104628977A (en) | Preparation method of tripolycyanamide-carbamide-formaldehyde resin adhesive | |
| CN109867761B (en) | Wood adhesive resin and preparation method thereof | |
| CN104493948B (en) | A kind of preparation method of high-moisture percentage particieboard | |
| NO833915L (en) | PROCEDURE FOR MANUFACTURING CARTRIDGES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190322 |
|
| WD01 | Invention patent application deemed withdrawn after publication |