CN110903451A - Preparation method of urea-formaldehyde resin with high prepressing performance and low molar ratio - Google Patents
Preparation method of urea-formaldehyde resin with high prepressing performance and low molar ratio Download PDFInfo
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- CN110903451A CN110903451A CN201911150417.5A CN201911150417A CN110903451A CN 110903451 A CN110903451 A CN 110903451A CN 201911150417 A CN201911150417 A CN 201911150417A CN 110903451 A CN110903451 A CN 110903451A
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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
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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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
- C09J161/22—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
Abstract
The invention discloses a preparation method of urea-formaldehyde resin with high prepressing performance and low molar ratio, which comprises the following core technical points: the method is characterized in that formaldehyde and urea with low molar ratio are used as raw materials, hyperbranched hydroxymethyl melamine surface modified nanofiber (NMP-CNF) is used as a catalyst, and urea formaldehyde resin is synthesized by a weak acid-weak base-weak acid-weak base acidic charging twice polycondensation process.
Description
Technical Field
The invention relates to the field of urea-formaldehyde resin, in particular to a preparation method of urea-formaldehyde resin with high prepressing property and low molar ratio.
Background
In 2018, the yield of the solid wood composite floor reaches 2.03 hundred million square meters in China, more than 90 percent of melamine modified urea-formaldehyde resin adhesive (MUF resin) is used, and the MUF resin is largely used in the solid wood composite floor due to incomparable advantages of other resins, such as sufficient raw materials, low price, good water solubility, light glue line color and the like. But the fatal shortcoming is that the glued artificial board has formaldehyde release problem, especially in the floor heating environment.
At present, the method for reducing the formaldehyde emission of the solid wood composite floor mainly comprises the following steps: 1) modifying urea-formaldehyde resin adhesive with low molar ratio; 2) adding a formaldehyde catching agent into the modified urea-formaldehyde resin adhesive; 3) carrying out post-treatment on the artificial board; 4) other environment-friendly adhesives are adopted. However, these techniques have various drawbacks. For example: 1) although the formaldehyde emission of the artificial board product can be effectively reduced by adopting the low-molar-ratio modified urea-formaldehyde resin adhesive, the bonding strength of the product is sharply reduced, and the use requirement cannot be met; and can result in extended curing times and reduced production efficiency; 2) the formaldehyde catching agent is added into the urea-formaldehyde resin adhesive for the artificial board, so that the free formaldehyde emission of the artificial board can be effectively reduced, but the bonding strength of the artificial board is often reduced; meanwhile, the price of the common formaldehyde catching agent is often far higher than that of the urea formaldehyde resin adhesive, and the addition of the formaldehyde catching agent improves the product cost and reduces the product competitiveness; 3) the artificial board is post-treated, such as preparing an environment-friendly artificial board by adopting an ammonia gas vacuum method and treating the artificial board by adopting a formaldehyde absorption agent, so that the artificial board has complex manufacturing process, the production cost is obviously improved, and in addition, the formaldehyde is released for a long time and rebounds to a certain degree; 4) due to the adoption of other environment-friendly adhesives such as isocyanate adhesives, the production cost of the artificial board is greatly increased, the difficulty of the production process is increased, and the artificial board is unacceptable to enterprises and users; the artificial board prepared by the common protein adhesive has low bonding strength, poor water resistance, easy mildew formation, poor gluing performance and easy glue failure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of urea-formaldehyde resin with high prepressing performance and low molar ratio, which takes formaldehyde and urea with low molar ratio as raw materials, utilizes hyperbranched hydroxymethyl melamine surface modified nanofiber (NMP-CNF) as a catalyst and synthesizes urea-formaldehyde resin by a twice polycondensation process of 'weak acid-weak base-weak acid-weak base' acidic charging so as to solve the problems in the technical background.
The purpose of the invention is realized by the following technical scheme:
a preparation method of urea-formaldehyde resin with high prepressing property and low molar ratio comprises the following preparation steps:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.6-1.7 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adding a catalyst with the monomer mass percentage of 0.5-1.0%, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to ensure that the molar ratio of the formaldehyde to the urea is 0.98-1.08 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
Further, in step S1, the formaldehyde is a formaldehyde solution with a mass concentration of 37%.
Further, in steps S1-S3, the pH is adjusted using sodium hydroxide or formic acid.
Further, in step S1, the catalyst is hyperbranched methylolmelamine surface-modified nanofiber (NMP-CNF), wherein the preparation method of the catalyst comprises the following preparation steps:
1) carrying out high-pressure homogenization treatment on the CNF suspension by using a high-pressure homogenizer, wherein the pressure of the high-pressure homogenizer is 30-40MPa, the emulsifying power is 8-10MPa, and then carrying out ultrasonic dispersion treatment by using an ultrasonic cell disruptor (the ultrasonic time is 30min, the ultrasonic power is 40%) to obtain uniformly dispersed CNF dispersion liquid;
2) adding 2g of formaldehyde and 5g of distilled water into a 50mL flask, adjusting the pH value to 8-9, adding 1g of melamine, heating to 90 ℃ in a water bath environment for 15min, keeping the pH value and the temperature unchanged, and continuing to react for 30min to obtain HMP;
3) adding 100g of CNF dispersion liquid prepared in the step 1) and 15g of HMP solution obtained in the step 2) into a 250mL three-neck flask for mixing reaction, adjusting the pH value to 9 by using 20% NaOH by mass, stirring and reacting at 80 ℃ for 60min, cooling to 40 ℃ and keeping the pH value to 8-9, and finally carrying out centrifugal rinsing to obtain the catalyst (NMP-CNF).
Further, the "high-pressure homogenization treatment of the CNF suspension using the high-pressure homogenizer" is repeated three times.
The invention has the beneficial effects that: the invention adopts formaldehyde and urea with low molar ratio as raw materials, uses hyperbranched hydroxymethyl melamine surface modified nanofiber (NMP-CNF) as a catalyst, and synthesizes the urea-formaldehyde resin by a twice polycondensation process of 'weak acid-weak base-weak acid-weak base' acidic charging.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
Example 1:
a preparation method of urea-formaldehyde resin with high prepressing property and low molar ratio comprises the following preparation steps:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.6-1.7 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adding a catalyst with the monomer mass percentage of 0.5-1.0%, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to ensure that the molar ratio of the formaldehyde to the urea is 0.98-1.08 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
Further, in step S1, the formaldehyde is a formaldehyde solution with a mass concentration of 37%.
Further, in steps S1-S3, the pH is adjusted using sodium hydroxide or formic acid.
Further, in step S1, the catalyst is hyperbranched methylolmelamine surface-modified nanofiber (NMP-CNF), wherein the preparation method of the catalyst comprises the following preparation steps:
1) carrying out high-pressure homogenization treatment on the CNF suspension by using a high-pressure homogenizer, wherein the pressure of the high-pressure homogenizer is 30-40MPa, the emulsifying power is 8-10MPa, and then carrying out ultrasonic dispersion treatment by using an ultrasonic cell disruptor (the ultrasonic time is 30min, the ultrasonic power is 40%) to obtain uniformly dispersed CNF dispersion liquid;
2) adding 2g of formaldehyde and 5g of distilled water into a 50mL flask, adjusting the pH value to 8-9, adding 1g of melamine, heating to 90 ℃ in a water bath environment for 15min, keeping the pH value and the temperature unchanged, and continuing to react for 30min to obtain HMP;
3) adding 100g of CNF dispersion liquid prepared in the step 1) and 15g of HMP solution obtained in the step 2) into a 250mL three-neck flask for mixing reaction, adjusting the pH value to 9 by using 20% NaOH by mass, stirring and reacting at 80 ℃ for 60min, cooling to 40 ℃ and keeping the pH value to 8-9, and finally carrying out centrifugal rinsing to obtain the catalyst (NMP-CNF).
Further, the "high-pressure homogenization treatment of the CNF suspension using the high-pressure homogenizer" is repeated three times.
Example 2:
a preparation method of urea-formaldehyde resin with high prepressing property and low molar ratio comprises the following preparation steps:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.6 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adding a catalyst with the monomer mass percentage of 0.5%, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to enable the molar ratio of formaldehyde to urea to be 0.98 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH to be =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
The quality indexes of the obtained urea resin are shown in the following table:
example 3:
a preparation method of urea-formaldehyde resin with high prepressing property and low molar ratio comprises the following preparation steps:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.7 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, adding a catalyst with the monomer mass percentage of 1.0% after heat preservation for 20 minutes, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to enable the molar ratio of formaldehyde to urea to be 1.08 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH to be =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
The quality indexes of the obtained urea resin are shown in the following table:
comparative example 1:
the preparation method of the urea-formaldehyde resin with high prepressing performance and low molar ratio is different from that of the urea-formaldehyde resin in the embodiment 2 in that:
the method is characterized by comprising the following steps of without adding a catalyst:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.6 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to enable the molar ratio of formaldehyde to urea to be 0.98 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH to be =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
Comparative example 2:
a method for preparing urea-formaldehyde resin with high pre-pressure and low molar ratio, which is different from the method of the embodiment 3 in that:
the method is characterized by comprising the following steps of without adding a catalyst:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.7 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to enable the molar ratio of formaldehyde to urea to be 1.08 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH to be =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
Comparative example 3:
the comparative example is a preparation method of a common urea-formaldehyde resin, and the specific preparation method comprises the following steps:
(1) preparing materials according to a molar ratio of 1.08 (formaldehyde: urea), then putting formaldehyde into a reaction kettle, adjusting the pH value to 8.0 by using alkaline liquor, adding a first batch of urea, heating to 90 ℃ within 1 hour, preserving heat for 1 hour, and keeping the pH value to 7.5-8.0;
(2) controlling the pH value to be 3.8-4.2 by acid liquor, and reacting at 95 ℃ until the viscosity is: coating a 4-cup for 24-27s (25 ℃), adding a second batch of urea, preserving the temperature for 30 minutes, and adjusting the pH value to 7.5-8.0 by using alkali liquor;
(3) adding the third batch of urea, reacting for 30 minutes, cooling to 35 ℃, adjusting the pH value to 7.5-8.0 by using alkali liquor, and discharging to obtain the urea.
The quality indexes of the obtained urea resin are shown in the following table:
the urea-formaldehyde resins prepared in the above examples 2-3 and comparative examples 1-3 were added with 1% ammonium chloride and 1% citric acid, respectively, then 30% flour was added, and then the eucalyptus plywood was manufactured by the conventional method to obtain five eucalyptus plywood floors with different urea-formaldehyde resins on the surface, and the five eucalyptus plywood floors were subjected to performance tests according to GB/T17657-1999 "Experimental methods for physical and chemical properties of artificial boards and veneers", and the test results are shown in the following table:
experimental results show that the urea-formaldehyde resin prepared by the method can effectively improve the prepressing property of the adhesive, reduce the formaldehyde release amount of the plywood, improve the water-resistant bonding performance and meet the strength requirement of the solid wood composite floor.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. The preparation method of the urea-formaldehyde resin with high prepressing performance and low molar ratio is characterized by comprising the following preparation steps:
s1, putting formaldehyde into a reaction kettle, adding a first batch of urea to enable the molar ratio of the formaldehyde to the urea to be 1.6-1.7 (formaldehyde: urea), adjusting the pH value to be 6.0, heating to 90 ℃ within 30 minutes, keeping the pH value at 6.0, keeping the temperature for 20 minutes, adding a catalyst with the monomer mass percentage of 0.5-1.0%, keeping the temperature for 20 minutes, adjusting the pH value to be 8.0, and keeping the temperature for 20 minutes;
s2, controlling the pH value to be 5.0, and controlling the temperature to be 90 ℃ to react until the viscosity is: coating in a 4-cup for 20s (25 ℃), adding a second batch of urea to make the molar ratio of formaldehyde to urea be 1.35 (formaldehyde: urea), adjusting the pH value to be 5.5, and reacting until the viscosity: coating the mixture in a 4-cup for 25-26s (25 ℃), and adjusting the pH value to 8.0;
s3, adding a third batch of urea to ensure that the molar ratio of the formaldehyde to the urea is 0.98-1.08 (formaldehyde: urea), reacting for 30 minutes, adjusting the pH =8, cooling to 40 ℃, and discharging to obtain the urea formaldehyde resin.
2. The method as claimed in claim 1, wherein the formaldehyde solution is 37% by mass in step S1.
3. The method of claim 1, wherein the pH of the urea-formaldehyde resin is adjusted by sodium hydroxide or formic acid in steps S1-S3.
4. The method of claim 1, wherein in step S1, the catalyst is hyperbranched hydroxymethylmelamine surface-modified nanofiber (NMP-CNF), and the method of preparing the catalyst comprises the following steps:
1) carrying out high-pressure homogenization treatment on the CNF suspension by using a high-pressure homogenizer, wherein the pressure of the high-pressure homogenizer is 30-40MPa, the emulsifying power is 8-10MPa, and then carrying out ultrasonic dispersion treatment by using an ultrasonic cell disruptor (the ultrasonic time is 30min, the ultrasonic power is 40%) to obtain uniformly dispersed CNF dispersion liquid;
2) adding 2g of formaldehyde and 5g of distilled water into a 50mL flask, adjusting the pH value to 8-9, adding 1g of melamine, heating to 90 ℃ in a water bath environment for 15min, keeping the pH value and the temperature unchanged, and continuing to react for 30min to obtain HMP;
3) adding 100g of CNF dispersion liquid prepared in the step 1) and 15g of HMP solution obtained in the step 2) into a 250mL three-neck flask for mixing reaction, adjusting the pH value to 9 by using 20% NaOH by mass, stirring and reacting at 80 ℃ for 60min, cooling to 40 ℃ and keeping the pH value to 8-9, and finally carrying out centrifugal rinsing to obtain the catalyst (NMP-CNF).
5. The method for preparing urea-formaldehyde resin with high pre-pressure and low molar ratio as claimed in claim 4, wherein the step 1) of "homogenizing CNF suspension with high pressure homogenizer" is repeated three times.
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