CN109867761B - Wood adhesive resin and preparation method thereof - Google Patents
Wood adhesive resin and preparation method thereof Download PDFInfo
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- CN109867761B CN109867761B CN201910164264.3A CN201910164264A CN109867761B CN 109867761 B CN109867761 B CN 109867761B CN 201910164264 A CN201910164264 A CN 201910164264A CN 109867761 B CN109867761 B CN 109867761B
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- 239000004840 adhesive resin Substances 0.000 title claims abstract description 34
- 229920006223 adhesive resin Polymers 0.000 title claims abstract description 34
- 239000002023 wood Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 161
- 239000004202 carbamide Substances 0.000 claims abstract description 50
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 40
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229920002396 Polyurea Polymers 0.000 claims description 26
- 239000008098 formaldehyde solution Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000005360 mashing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 239000011120 plywood Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000009615 deamination Effects 0.000 abstract description 3
- 238000006481 deamination reaction Methods 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 16
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 241000219000 Populus Species 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention provides a novel wood adhesive resin and a preparation method thereof, belonging to the technical field of wood adhesives. The preparation raw materials comprise: ethylenediamine, urea and formaldehyde; the molar ratio of urea to ethylenediamine is 2.0-2.5; the molar ratio of the formaldehyde to the urea is 0.85-1.0. In the preparation process, firstly, the deamination condensation reaction is carried out on ethylenediamine and urea under the conditions of no solvent and no catalyst to synthesize urea-ethylenediamine polyamide, and then the urea-ethylenediamine polyamide and formaldehyde are synthesized to prepare the final wood adhesive resin; the finally prepared wood adhesive resin is milky uniform liquid in appearance, the solid content is 60-65%, and the storage period is more than 7 days. The urea-ethylenediamine-formaldehyde resin wood adhesive provided by the invention has the advantages of simple synthesis method, low curing temperature, excellent performance, low formaldehyde emission and the like, and can be used for producing artificial boards such as plywood, shaving board and the like.
Description
Technical Field
The application belongs to the technical field of wood adhesives, and particularly relates to a wood adhesive resin and a preparation method thereof.
Background
Urea-formaldehyde resin (UF) is the largest amount of wood adhesive resin used in the current wood-based panel industry due to its great cost advantage. However, urea-formaldehyde resin has the significant defects of poor durability of glued products, large formaldehyde emission and the like. Along with social progress, health and environmental awareness of people are increasingly strengthened, and countries in the world have developed strict formaldehyde release standards of artificial board products in succession, so that the application of the urea-formaldehyde resin faces severe challenges. In order to reduce the formaldehyde emission of the artificial board, a low-molar-ratio synthesis process is generally adopted at present. The molar ratio of formaldehyde to urea even falls to the theoretical limit, i.e. around 1.0. However, the formaldehyde emission is significantly reduced and the resin properties are also drastically deteriorated. Among these, the prolonged curing time and the reduced water resistance are two direct results of the reduced molar ratio. The prolonged curing time leads to low production efficiency, and higher curing temperature is necessary to ensure production efficiency, which leads to increased energy consumption. The decrease of the water resistance enables the urea resin to be applied only to the production of indoor artificial boards.
In addition, the synthesis of conventional urea formaldehyde resins involves two main stages: 1) formaldehyde and urea are subjected to addition reaction under an alkaline condition to generate micromolecular hydroxymethyl urea; 2) the hydroxymethyl urea is subjected to polycondensation reaction under an acidic condition to generate resin molecules with larger molecular weight. This process is generally described briefly by "addition-polycondensation". In the urea-formaldehyde resin molecule before curing, the urea structural unit is formed by methylene bridge bond (-CH)2-) and methylene ether linkage (-CH)2-O-CH2-) linkage, both structures are generated from formaldehyde, consuming 40% -50% of the formaldehyde. The remaining about 20-30% of formaldehyde forms a branched structure (-N (C) 2-CH-)-CH2-NH-) or (-N- 2CH-)-CH2-N(- 2CH-) and the remaining formaldehyde is present as hydroxymethyl and free formaldehyde. The fully cured resin exists primarily in a condensed structure. Free formaldehyde can be released in a short time, but due to the low chemical stability of the polycondensation structure, the gradual depolymerization and release of formaldehyde over the life cycle is a slow process, constituting a long-term potential threat to human health.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present application provides a wood adhesive resin and a method for preparing the same.
The wood adhesive resin provided by the invention comprises the following preparation raw materials: ethylenediamine, urea and formaldehyde; the molar ratio of urea to ethylenediamine is 2.0-2.5; the molar ratio of the formaldehyde to the urea is 0.85-1.0. The preparation method of the wood adhesive resin comprises the following steps:
step one, mixing urea and ethylenediamine in a reaction container at room temperature, and controlling the molar ratio of the urea to the ethylenediamine to be 2.0-2.5; continuously stirring the reactants, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction at 110 ℃, and absorbing overflowed ammonia gas by an ammonia gas absorption device in the reaction process; stopping stirring when reactants in the reaction container are changed from liquid to solid, raising the temperature of the oil bath to 115 ℃, continuing to perform heat preservation reaction for 3 hours, and then cooling the reactants to obtain white solid;
step two, taking out the white solid obtained in the step one, mashing the white solid into granules, placing the granules into an open container, and deaminating the granules for 5 hours at the temperature of 60 ℃ to obtain urea-ethylenediamine polyurea solid;
calculating the use amount of a formaldehyde solution with the concentration of 37% according to the use amount of urea used for synthesizing the urea-ethylenediamine polyurea, and enabling the molar ratio of formaldehyde to urea to be 0.85-1.0; weighing the formaldehyde solution according to the calculated amount of the formaldehyde solution, and adjusting the pH of the formaldehyde solution to 8.0-9.0 by using a NaOH solution at room temperature;
step four, heating the formaldehyde solution with the pH value adjusted to 8.0-9.0 to 40-50 ℃ in a water bath, adding the urea-ethylenediamine polyurea solid synthesized in the step two in the stirring process, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling at room temperature to obtain a milky uniform liquid with the pH value of 7.5-8.0, wherein the liquid is the prepared wood adhesive resin: urea-ethylenediamine-formaldehyde adhesive resin.
The method for preparing a wood adhesive resin as described above, wherein the urea-ethylenediamine polyurea molecule synthesized through the step two has-CH2-CH2-NH-CO-NH-repeat structure with segment end-CH2-CH2-NH-CO-NH2or-CH2-CH2-NH2And (5) structure.
The preparation method of the wood adhesive resin comprises the step four, wherein the solid content of the urea-ethylenediamine-formaldehyde adhesive resin prepared in the step four is 60-65%, and the storage period is at least 7 days.
The wood adhesive resin and the preparation method thereof provided by the invention have the following advantages:
1. the synthesis scheme of synthesizing polyurea macromolecules by the polycondensation reaction of urea and ethylenediamine and preparing adhesive resin by the reaction of polyurea and formaldehyde greatly reduces the using amount of formaldehyde and the formaldehyde release amount of artificial board products in the use period.
2. The curing temperature of the prepared resin is obviously lower than that of the traditional urea-formaldehyde resin. Taking the example of pressing the three-layer plywood by using 2mm poplar veneers, when the hot pressing time is 5 minutes, the complete curing of the resin can be realized only when the hot pressing temperature of the traditional urea-formaldehyde resin is generally over 140 ℃, but the resin prepared by the invention can be completely cured at about 80 ℃, so that the energy cost can be greatly saved in the practical application, and the production efficiency is improved.
3. The prepared resin has excellent water resistance. The traditional urea-formaldehyde resin has poor water resistance and cannot meet the use requirement under high humidity conditions. The plywood pressed by the resin prepared by the invention can reach the requirement of national standard GB/T9846-2015 ordinary plywood on the water resistance of the second class of boards, and can meet the use requirement of artificial board products in high-humidity environment.
Detailed Description
The following embodiments will be described in detail with reference to the accompanying examples, so that the implementation process of how to apply the technical means to solve the technical problems and achieve the technical effects of the present application can be fully understood and implemented.
The contradiction between formaldehyde release and performance is solved, and the development of resin is a key technical guarantee for realizing the upgrading of the artificial board industry. From resin structure analysis, the main reason why the reduction in the molar ratio leads to deterioration in performance is that the use of an excessive amount of urea greatly reduces the degree of branching of the resin molecules. The reduction of the branching degree slows down the curing speed of the resin, and simultaneously, a compact cross-linked network structure is difficult to form, thereby causing the reduction of the bonding strength, especially the rapid deterioration of the water resistance. Therefore, the key to the innovation of the synthetic technology is to reduce the amount of formaldehyde and ensure higher branching degree of resin molecules.
The invention aims to provide a wood adhesive resin, namely urea-ethylenediamine-formaldehyde resin. The resin has the advantages of low curing temperature, excellent water resistance, low formaldehyde release amount and the like, can solve the contradiction between the performance of the traditional urea-formaldehyde resin and the formaldehyde release amount, and realizes the great improvement of the overall performance of the adhesive. The wood adhesive resin provided by the invention comprises the following raw materials: ethylenediamine, urea and formaldehyde; the molar ratio of urea to ethylenediamine is 2.0-2.5; the molar ratio of the formaldehyde to the urea is 0.85-1.0.
Specifically, the preparation method of the wood adhesive resin provided by the invention can comprise the following steps:
step one, mixing urea and ethylenediamine in a reaction container at room temperature, and controlling the molar ratio of the urea to the ethylenediamine to be 2.0-2.5; continuously stirring the reactants, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction at 110 ℃, and absorbing overflowed ammonia gas by an ammonia gas absorption device in the reaction process; stopping stirring when reactants in the reaction container are changed from liquid to solid, raising the temperature of the oil bath to 115 ℃, continuing to perform heat preservation reaction for 3 hours, and then cooling the reactants to obtain white solid.
And step two, taking out the white solid obtained in the step one, mashing the white solid into granules, placing the granules into an open container, and deaminating the granules for 5 hours at the temperature of 60 ℃ to obtain the urea-ethylenediamine polyurea solid.
The urea-ethylenediamine polyurea molecule synthesized by the step two has-CH2-CH2-NH-CO-NH-repeat structure with segment end-CH2-CH2-NH-CO-NH2or-CH2-CH2-NH2And (5) structure.
Calculating the use amount of a formaldehyde solution with the concentration of 37% according to the use amount of urea used for synthesizing the urea-ethylenediamine polyurea, and enabling the molar ratio of formaldehyde to urea to be 0.85-1.0; weighing the formaldehyde solution according to the calculated using amount of the formaldehyde solution, and adjusting the pH of the formaldehyde solution to 8.0-9.0 by using a NaOH solution at room temperature.
Step four, heating the formaldehyde solution with the pH value adjusted to 8.0-9.0 to 40-50 ℃ in a water bath, adding the urea-ethylenediamine polyurea solid synthesized in the step two in the stirring process, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling at room temperature to obtain a milky uniform liquid with the pH value of 7.5-8.0, wherein the liquid is the prepared wood adhesive resin: urea-ethylenediamine-formaldehyde adhesive resin.
The solid content of the urea-ethylenediamine-formaldehyde adhesive resin prepared in the fourth step is 60-65%, and the storage period is at least 7 days.
Based on the deamination condensation reaction of fatty amine and amide, urea and ethylenediamine are used for deamination condensation, and the connection of urea structural units is realized by using the ethylenediamine to form linear polymer molecules, so that a polycondensation structure-HN-CO-NH-CH similar to urea-formaldehyde resin molecules is obtained2-CH2-NH-CO-NH-, but this structure is typical of polyurea, with much higher stability than normal urea formaldehyde resins. The amino group in the condensation polymerization structure still has the property similar to the urea amino group, and can generate addition reaction with formaldehyde to form a branched chain structure. This synthetic scheme can be described as "condensation-addition," which completely subverts the synthetic route of traditional urea-formaldehyde resins.
Since the function of linking urea is realized by ethylenediamine, the amount of formaldehyde used for forming branched chains at a later stage can be greatly reduced. Compared with the traditional urea resin, the resin has the following obvious advantages: firstly, the formaldehyde dosage is greatly reduced, so that the formaldehyde emission in the use process of the artificial board product can be reduced; secondly, the molecular main structure is a very stable polyurea structure and does not contain easily hydrolyzed ether bonds, so that the resin has excellent water resistance, and the dimensional stability of the plate in a humid environment is ensured; thirdly, the molecular weight of the traditional urea-formaldehyde resin is mainly distributed between 200 and 600, and the molecular weight of the resin is distributed between 300 and 1000. The higher molecular weight and higher degree of branching allows curing to occur at lower temperatures. In addition, the condensation of urea and ethylenediamine can be carried out without a catalyst, and the reaction of polyurea and formaldehyde is carried out under a weakly alkaline condition without adopting acid as a catalyst, so that the protection requirement of a reaction container on corrosion is lowered.
In specific application, the adhesive resin provided by the invention is used for manufacturing poplar three-layer boards, and the physical and chemical performance test method of artificial boards and decorative artificial boards is carried out according to the national standard GB/T17657-20131m specified in3And (4) testing the formaldehyde emission of the plate by a weather box method. The test result shows that the formaldehyde emission is less than 0.124mg/m2And meets the limit regulation of the national standard GB 18580-2017 Formaldehyde emission limit in artificial boards and products thereof for interior decoration and finishing materials.
The poplar three-layer board prepared by the adhesive resin provided by the invention is tested according to the national standard GB/T17657 plus 2013 physical and chemical property test method for artificial boards and veneers, and the wet bonding strength of a test piece after being soaked in hot water at 63 ℃ for 3 hours is more than 0.7Mpa, so that the water resistance requirement of the national standard GB/T9846 plus 2015 common plywood on II-type boards can be met.
The following is an application example of the technical scheme provided by the invention:
example 1:
the urea, the ethylenediamine and the formaldehyde are taken as raw materials for synthesis, wherein:
a. mixing urea (U) and ethylenediamine (E) in a reaction vessel at room temperature under stirring, controlling the molar ratio U/E of urea to ethylenediamine to be 2.0, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction, and absorbing overflowing ammonia gas by an ammonia gas absorption device in the reaction process. Stopping stirring when the reaction liquid in the container is changed from liquid to solid, simultaneously raising the temperature of the oil bath to 115 ℃, and continuing the heat preservation reaction for 3 hours. Cooling to obtain white solid product.
b. Taking out the white solid, mashing the white solid into granules, placing the granules in an open container, and deaminating the granules at the temperature of 60 ℃ for 5 hours to obtain urea-ethylenediamine polyurea for later use.
c. The amount of formaldehyde solution used was calculated to be 37% based on the urea used to synthesize the polyurea, so that the molar ratio F/U of formaldehyde to urea was 0.85. And (3) adjusting the pH value of the formaldehyde solution to about 8.0-9.0 by using NaOH solution at room temperature.
d. Heating the formaldehyde solution in a water bath to 40-50 ℃, adding metered urea-ethylenediamine polyurea solid while stirring, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling the product at room temperature to obtain milky uniform liquid with the pH of 7.5-8.0. The liquid is urea-ethylenediamine-formaldehyde adhesive resin.
Example 2:
is synthesized by urea, ethylenediamine and formaldehyde, wherein:
a. mixing urea (U) and ethylenediamine (E) in a reaction vessel at room temperature under stirring, controlling the molar ratio U/E of urea to ethylenediamine to be 2.2, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction, and absorbing overflowing ammonia gas by an ammonia gas absorption device in the reaction process. Stopping stirring when the reaction liquid in the container is changed from liquid to solid, simultaneously raising the temperature of the oil bath to 115 ℃, and continuing the heat preservation reaction for 3 hours. Cooling to obtain white solid product.
b. Taking out the white solid, mashing the white solid into granules, placing the granules in an open container, and deaminating the granules at the temperature of 60 ℃ for 5 hours to obtain urea-ethylenediamine polyurea for later use.
c. The amount of formaldehyde solution used was calculated to be 37% by concentration based on the urea used to synthesize the polyurea, so that the molar ratio F/U of formaldehyde to urea was 0.9. And (3) adjusting the pH value of the formaldehyde solution to about 8.0-9.0 by using NaOH solution at room temperature.
d. Heating the formaldehyde solution in a water bath to 40-50 ℃, adding metered urea-ethylenediamine polyurea solid while stirring, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling the product at room temperature to obtain milky uniform liquid with the pH of 7.5-8.0. The liquid is urea-ethylenediamine-formaldehyde adhesive resin.
Example 3:
is synthesized by urea, ethylenediamine and formaldehyde, wherein:
a. mixing urea (U) and ethylenediamine (E) in a reaction vessel at room temperature under stirring, controlling the molar ratio U/E of urea to ethylenediamine to be 2.5, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction, and absorbing overflowing ammonia gas by an ammonia gas absorption device in the reaction process. Stopping stirring when the reaction liquid in the container is changed from liquid to solid, raising the temperature of the oil bath to 115 ℃, and continuing the heat preservation reaction for 3 hours. Cooling to obtain white solid product.
b. Taking out the white solid, mashing the white solid into granules, placing the granules in an open container, and deaminating the granules at the temperature of 60 ℃ for 5 hours to obtain urea-ethylenediamine polyurea for later use.
c. The amount of formaldehyde solution having a concentration of 37% was calculated on the basis of urea used for synthesizing polyurea so that the molar ratio F/U of formaldehyde to urea was 1.0. And (3) adjusting the pH value of the formaldehyde solution to about 8.0-9.0 by using NaOH solution at room temperature.
d. Heating the formaldehyde solution in a water bath to 40-50 ℃, adding metered urea-ethylenediamine polyurea solid while stirring, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling the product at room temperature to obtain milky uniform liquid with the pH of 7.5-8.0. The liquid is urea-ethylenediamine-formaldehyde adhesive resin.
The adhesives prepared in the examples 1-3 are respectively taken, poplar veneers with the thickness of 2mm are used for manufacturing three-layer plywood, and the 1m plywood is prepared according to the specification of GB/T17657-2013 physicochemical property test method for artificial boards and decorative artificial boards3The formaldehyde emission of the plate is detected by a weather box method, and the detection result shows that the formaldehyde emission is 0.08-0.10 mg/m3。
The adhesives prepared in the embodiments 1-3 are respectively taken to prepare a three-layer plywood by using poplar veneers with the thickness of 2mm, and the adhesive application amount is 250-2(the amount of glue applied to the two sides of the core layer) according to the national standard GB/T17657 plus 2013 physicochemical property test method for artificial boards and decorative artificial boards, the physical and mechanical properties of the board are tested, and the water resistance of the board is mainly tested. The specific results are as follows:
the hot pressing temperature is 80 ℃, the hot pressing time is 5 minutes, and the wet bonding strength of the test piece after being soaked in hot water at 63 ℃ for 3 hours is 0.80-1.20 Mpa.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the present application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of numerous other combinations, modifications, and variations within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (2)
1. The preparation method of the wood adhesive resin is characterized in that the raw materials for preparing the wood adhesive resin comprise: ethylenediamine, urea and formaldehyde; the molar ratio of urea to ethylenediamine is 2.0-2.5; the molar ratio of the formaldehyde to the urea is 0.85-1.0;
the preparation method of the wood adhesive resin comprises the following steps:
step one, mixing urea and ethylenediamine in a reaction container at room temperature, and controlling the molar ratio of the urea to the ethylenediamine to be 2.0-2.5; continuously stirring the reactants, continuously heating to 110 ℃ in an oil bath, carrying out heat preservation reaction at 110 ℃, and absorbing overflowed ammonia gas by an ammonia gas absorption device in the reaction process; stopping stirring when reactants in the reaction container are changed from liquid to solid, raising the temperature of the oil bath to 115 ℃, continuing to perform heat preservation reaction for 3 hours, and then cooling the reactants to obtain white solid;
step two, taking out the white solid obtained in the step one, mashing the white solid into granules, placing the granules into an open container, and deaminating the granules for 5 hours at the temperature of 60 ℃ to obtain urea-ethylenediamine polyurea solid;
calculating the use amount of a formaldehyde solution with the concentration of 37% according to the use amount of urea used for synthesizing the urea-ethylenediamine polyurea, and enabling the molar ratio of formaldehyde to urea to be 0.85-1.0; weighing the formaldehyde solution according to the calculated amount of the formaldehyde solution, and adjusting the pH of the formaldehyde solution to 8.0-9.0 by using a NaOH solution at room temperature;
step four, heating the formaldehyde solution with the pH value of 8.0-9.0 to 40-50 ℃ in a water bath, adding the urea-ethylenediamine polyurea solid synthesized in the step two in the stirring process, simultaneously heating the water bath to 80 ℃, continuously reacting, stopping heating when the white solid disappears and the reaction liquid becomes transparent, and naturally cooling at room temperature to obtain a milky uniform liquid with the pH value of 7.5-8.0, wherein the milky uniform liquid is the prepared wood adhesive resin: urea-ethylenediamine-formaldehyde binder resin;
synthesized by the second stepHas a-CH-urea-ethylenediamine polyurea molecule2-CH2-NH-CO-NH-repeat structure with segment end-CH2-CH2-NH-CO-NH2or-CH2-CH2-NH2And (5) structure.
2. The method for preparing wood adhesive resin according to claim 1, wherein the urea-ethylenediamine-formaldehyde adhesive resin prepared in the fourth step has a solid content of 60 to 65% and a storage period of at least 7 days.
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| CN111718273B (en) * | 2020-07-22 | 2022-11-08 | 万华化学集团股份有限公司 | Ethylene diamine tetraacetic acid ester substance and application thereof in preparation of polyvinyl chloride anti-sticking agent |
| CN113980269A (en) * | 2021-07-22 | 2022-01-28 | 西南林业大学 | Melamine-diamine or polyamine-urea ternary copolycondensation thermosetting resin and preparation method and application thereof |
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