CN109180890B - Method for preparing low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues - Google Patents

Method for preparing low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues Download PDF

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CN109180890B
CN109180890B CN201810716674.XA CN201810716674A CN109180890B CN 109180890 B CN109180890 B CN 109180890B CN 201810716674 A CN201810716674 A CN 201810716674A CN 109180890 B CN109180890 B CN 109180890B
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alkali solution
ethanol fermentation
cellulosic ethanol
fermentation residues
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CN109180890A (en
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袁同琦
孙润仓
杨昇
庞博
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Beijing Forestry University
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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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas
    • 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
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps: mixing the cellulosic ethanol fermentation residues with a first alkali solution, and activating to obtain a first activated product; carrying out a first reaction on the first activated product and phenol to obtain a second activated product; carrying out a second reaction on the second activation product, a second alkali solution and the first formaldehyde solution to obtain a first polycondensation product; carrying out a third reaction on the first polycondensation product, a third alkali solution and a second formaldehyde solution to obtain a second polycondensation product; carrying out a fourth reaction on the second polycondensation product, a fourth alkali solution and a third furfural solution to obtain a third polycondensation product; and carrying out a fifth reaction on the third polycondensation product, a fifth alkali solution and urea, and cooling to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive. The adhesive disclosed by the invention takes cellulosic ethanol fermentation residues as a raw material, reduces the dependence on petrochemical resources, and improves the overall economic benefit of the artificial board industry.

Description

Method for preparing low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues
Technical Field
The invention relates to the field of wood adhesive preparation, in particular to a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues.
Background
Cellulosic ethanol refers to the conversion of various biomasses to fuel alcohol by fermentation of microorganisms. It can be used alone or mixed with gasoline to prepare ethanol gasoline as automobile fuel. The majority of the fuel ethanol produced industrially at present is prepared from food crops, and has scale limitation and unsustainability in the long term. The second generation of biofuel ethanol using lignocellulose as raw material is the key to determine the large-scale replacement of petroleum in the future. With the increasing aggravation of energy problems and the obvious highlighting of grain problems, various countries have been vigorously developing the technology of using lignocellulose as raw material cellulosic ethanol, and although the technology has a large investment, the technology has a more sustainable development prospect in the long-term development. A great deal of research on the method has been carried out in developed countries such as Europe and America, China also carries out a great deal of exploration in the aspect, and the way of large-scale production of the cellulosic ethanol is actively explored. Cellulosic ethanol production will produce large amounts of cellulosic ethanol fermentation residues rich in highly active lignin and highly crystalline cellulose with yields far exceeding the amount of cellulosic ethanol obtained, and therefore, rational utilization of the cellulosic ethanol is an important guarantee for ensuring the economic benefits of the lignocellulosic ethanol and promoting sustainable development thereof.
Along with the increasing crisis of petroleum resources in recent years, the price of petrochemical resources is continuously increased, which brings great influence to the phenolic resin adhesive industry depending on the petrochemical resources, and the continuous increase of the price of raw materials leads to the rise of finished products, thereby seriously limiting the sustainable development of the industry.
Disclosure of Invention
The invention mainly aims to provide a novel method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, and aims to solve the technical problems of low price and reduced formaldehyde release amount, so that the method is more practical.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues comprises the following steps:
mixing the cellulosic ethanol fermentation residues with a first alkali solution, and activating to obtain a first activated product;
carrying out a first reaction on the first activation product and phenol to obtain a second activation product;
carrying out a second reaction on the second activation product, a second alkali solution and a first formaldehyde solution to obtain a first polycondensation product;
carrying out a third reaction on the first polycondensation product, a third alkali solution and a second formaldehyde solution to obtain a second polycondensation product;
carrying out a fourth reaction on the second polycondensation product, a fourth alkali solution and a third furfural solution to obtain a third polycondensation product;
and carrying out a fifth reaction on the third polycondensation product, a fifth alkali solution and urea, and cooling to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the weight ratio of the cellulosic ethanol fermentation residues to the first alkali solution is 1: 0.8-1.5;
the activation temperature is 85-100 ℃, and the activation time is 0.5-1 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the weight ratio of the phenol to the cellulosic ethanol fermentation residues is 0.67-9: 1;
the temperature of the first reaction is 90-100 ℃, and the reaction time is 1-2 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the addition amount of the second alkali solution is 10-15% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the first formaldehyde solution is 25-35% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the second reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the addition amount of the third alkali solution is 5-10% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the second formaldehyde solution is 20-25% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the third reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the addition amount of the fourth alkali solution is 5-10% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the addition amount of the third furfural solution is 15-20% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the fourth reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the addition amount of the fifth alkali solution is 10-15% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the urea is 3-8% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the fifth reaction is 60-70 ℃, and the reaction time is 0.3-0.6 h.
Preferably, in the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues, the first alkali solution is a sodium hydroxide alkali solution, and the mass concentration of the first alkali solution is 5-10%;
the second alkali solution is sodium hydroxide alkali solution, and the mass concentration of the second alkali solution is 20-40%;
the third alkali solution is sodium hydroxide alkali solution, and the mass concentration of the third alkali solution is 20-40%;
the fourth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fourth alkali solution is 20-40%;
the fifth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fifth alkali solution is 20-40%;
the mass concentration of the formaldehyde solution is 30-50%.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The low-formaldehyde water-resistant copolycondensation resin adhesive provided by the invention is prepared by the method.
By means of the technical scheme, the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive by using the cellulosic ethanol fermentation residues at least has the following advantages:
1) the raw materials used in the invention contain a large proportion of waste residues in the cellulosic ethanol industry, so that the product is low in price and beneficial to popularization and use, and the large application of the raw materials can improve the overall economic benefit of the cellulosic ethanol industry, broaden the raw material sources of the traditional resin adhesive and relieve the dependence of the industry on petrochemical resources;
2) the cellulosic ethanol fermentation residues are firstly subjected to swelling treatment and then activated, so that the reaction activity can be enhanced, the substitution rate is improved, and the cost is reduced;
3) the process fully considers the characteristics of the raw materials, and designs reasonable activation steps, reaction systems and multi-step copolycondensation reaction flows according to the characteristics. The plywood prepared by the adhesive can reach the I-type board strength standard, and the formaldehyde emission meets the E0And (5) the requirement of a level limit amount.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description will be given to the specific embodiments, structures, characteristics and effects of the method for preparing the low-formaldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues according to the present invention with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention provides a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps:
mixing the cellulosic ethanol fermentation residues with a first alkali solution, and activating at 85-100 ℃ for 0.5-1h to obtain a first activated product;
mixing the first activation product with phenol, and reacting at 90-100 ℃ for 1-2h to obtain a second activation product;
mixing the second activation product with a second alkali solution and a first formaldehyde solution, and reacting at 80-90 ℃ for 0.5-1h to obtain a first polycondensation product;
mixing the first polycondensation product with a third alkali solution and a second formaldehyde solution, and reacting at 80-90 ℃ for 0.5-1h to obtain a second polycondensation product;
mixing the second polycondensation product with a fourth alkali solution and a third formaldehyde solution, and reacting at 80-90 ℃ for 0.5-1h to obtain a third polycondensation product;
and mixing the third polycondensation product with a fifth alkali solution and urea, reacting for 0.3-0.6h at 60-70 ℃, cooling and discharging to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
Preferably, the weight ratio of the cellulosic ethanol fermentation residue (in absolute dry solids) to the first alkali solution is 1: 0.8-1.5.
Preferably, the weight ratio of phenol to cellulosic ethanol fermentation residue (in absolute dry solids) is 0.67-9: 1.
Preferably, the addition amount of the second alkali solution is 10-15% of the mass sum of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid);
the addition amount of the first formaldehyde solution is 25-35% of the mass sum of phenol and cellulosic ethanol fermentation residues (calculated by absolute dry solid).
Preferably, the addition amount of the third alkali solution is 5-10% of the mass sum of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid);
the addition amount of the second formaldehyde solution is 20-25% of the mass sum of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid).
Preferably, the addition amount of the fourth alkali solution is 5-10% of the mass sum of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid);
the addition amount of the third furfural solution is 15-20% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid).
Preferably, the addition amount of the fifth alkali solution is 10-15% of the mass sum of the phenol and the cellulosic ethanol fermentation residue (calculated by absolute dry solid);
the addition amount of urea is 3-8% of the mass sum of the phenol and the cellulosic ethanol fermentation residues.
Preferably, the first alkali solution is sodium hydroxide alkali solution, and the mass concentration is 5-10%; wherein the mass of water in the first alkali solution is the sum of the mass of water in the ethanol fermentation residues and the mass of water added during preparation of the first alkali solution;
the second alkali solution is sodium hydroxide alkali solution, and the mass concentration of the second alkali solution is 20-40%;
the third alkali solution is sodium hydroxide alkali solution, and the mass concentration of the third alkali solution is 20-40%;
the fourth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fourth alkali solution is 20-40%;
the fifth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fifth alkali solution is 20-40%;
the mass concentration of the formaldehyde solution is 30-50%, and the mass concentration is preferably 37%.
Preferably, another embodiment of the present invention provides a low-formaldehyde water-resistant copolycondensation resin adhesive, which is prepared by the method. The viscosity of the low-aldehyde water-resistant copolycondensation resin adhesive is 115-200 mPas. The low-formaldehyde water-resistant copolycondensation resin adhesive is used for gluing the plywood, the plywood can reach the strength standard of class I boards, and the formaldehyde emission meets the E0And (5) the requirement of a level limit amount.
Example 1
The invention provides a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps:
mixing 36g of cellulosic ethanol fermentation residues with 50g of 5 wt% NaOH solution, and stirring at 90 ℃ for 1h to obtain a first activated product;
adding 23g of phenol into the first activated product, and fully reacting for 1h at 95 ℃ to obtain a second activated product;
adding 6.67g of 30 wt% NaOH aqueous solution and 20.42g of 37 wt% formaldehyde aqueous solution into the second activation product, and reacting at 80 ℃ for 1h to obtain a first polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 13.68g of 37 wt% formaldehyde aqueous solution into the first polycondensation product, and reacting at 80 ℃ for 1h to obtain a second polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 9.68g of 37 wt% formaldehyde aqueous solution into the second polycondensation product, and reacting at 80 ℃ for 1h to obtain a third polycondensation product;
and adding 7.83g of 30 wt% NaOH aqueous solution and 5g of urea into the third polycondensation product, reacting for 0.5h at 60 ℃, cooling and discharging to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
Another embodiment of the invention provides a low-formaldehyde water-resistant copolycondensation resin adhesive prepared by the method of embodiment 1. The low-aldehyde water-resistant copolycondensation resin adhesive of example 1 was measured for solid content, viscosity and pH as specified in GB/T14074-2006, and the results are shown in table 1.
Another embodiment of the present invention provides a poplar three-ply plywood, which is obtained by gluing the low-formaldehyde water-resistant copolycondensation resin adhesive of embodiment 1, wherein the gluing amount of the veneer is 280-2The hot pressing temperature is 145 ℃, the hot pressing pressure is 1MPa, and the hot pressing time is 1.5 min/mm.
The pressed plywood from example 1 was tested after 5-7 days at room temperature. The plywood of example 1 had a bond strength as measured by the fast test method for type i panels in GB/T9846-2004, i.e. boiling in boiling water for 3 hours, multiplied by a factor of 0.9, with the results shown in table 1, where the plywood strength is the test result for 14 test pieces, the numerator is the average bond strength, and the denominator is the lowest strength-highest strength; the formaldehyde emission was measured by the dryer method specified in 4.12 of GB/T17657-2013, and the results are shown in Table 1.
Example 2
The invention provides a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps:
mixing 36g of cellulosic ethanol fermentation residues with 50g of 10 wt% NaOH solution, and stirring at 90 ℃ for 0.5h to obtain a first activated product;
adding 23g of phenol into the first activated product, and fully reacting for 1h at 95 ℃ to obtain a second activated product;
adding 6.67g of 30 wt% NaOH aqueous solution and 20.42g of 37 wt% formaldehyde aqueous solution into the second activation product, and reacting at 90 ℃ for 1h to obtain a first polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 13.68g of 37 wt% formaldehyde aqueous solution into the first polycondensation product, and reacting at 90 ℃ for 0.8h to obtain a second polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 9.68g of 37 wt% formaldehyde aqueous solution into the second polycondensation product, and reacting at 90 ℃ for 0.5h to obtain a third polycondensation product;
and adding 7.83g of 30 wt% NaOH aqueous solution and 5g of urea into the third polycondensation product, reacting for 0.5h at 65 ℃, cooling and discharging to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
Another embodiment of the invention provides a low-formaldehyde water-resistant copolycondensation resin adhesive prepared by the method of embodiment 2. The low-aldehyde water-resistant copolycondensation resin adhesive of example 2 was measured for solid content, viscosity and pH as specified in GB/T14074-2006, and the results are shown in table 1.
Another embodiment of the present invention provides a poplar three-ply plywood, which is obtained by gluing the low-formaldehyde water-resistant copolycondensation resin adhesive of embodiment 2, wherein the gluing amount of the veneer is 280-316g/m2The hot pressing temperature is 145 ℃, the hot pressing pressure is 1MPa, and the hot pressing time is 1.5 min/mm.
The pressed plywood from example 2 was tested after 5-7 days at room temperature. The plywood of example 2 was boiled in boiling water for 3 hours according to the fast test method for class i boards in GB/T9846-2004, and the results were multiplied by a factor of 0.9, with the results shown in table 1, wherein the plywood strength was the test result for 14 test pieces, the numerator was the average bond strength, and the denominator was the lowest strength-highest strength; the formaldehyde emission was measured by the dryer method specified in 4.12 of GB/T17657-2013, and the results are shown in Table 1.
Example 3
The invention provides a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps:
mixing 36g of cellulosic ethanol fermentation residues with 36g of 5 wt% NaOH solution, and stirring at 90 ℃ for 1h to obtain a first activated product;
adding 23g of phenol into the first activated product, and fully reacting for 1h at 95 ℃ to obtain a second activated product;
adding 6.67g of 30 wt% NaOH aqueous solution and 20.42g of 37 wt% formaldehyde aqueous solution into the second activation product, and reacting at 85 ℃ for 0.8h to obtain a first polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 13.68g of 37 wt% formaldehyde aqueous solution into the first polycondensation product, and reacting at 85 ℃ for 0.8h to obtain a second polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 9.68g of 37 wt% formaldehyde aqueous solution into the second polycondensation product, and reacting at 85 ℃ for 0.8h to obtain a third polycondensation product;
and adding 7.83g of 30 wt% NaOH aqueous solution and 10g of urea into the third polycondensation product, reacting for 0.5h at 65 ℃, cooling and discharging to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
Another embodiment of the invention provides a low-formaldehyde water-resistant copolycondensation resin adhesive prepared by the method of embodiment 3. The low-aldehyde water-resistant copolycondensation resin adhesive of example 3 was measured for solid content, viscosity and pH as specified in GB/T14074-2006, and the results are shown in table 1.
Another embodiment of the present invention provides a poplar three-ply plywood, which is obtained by gluing the low-formaldehyde water-resistant copolycondensation resin adhesive of embodiment 3, wherein the gluing amount of the veneer is 280-316g/m2The hot pressing temperature is 145 ℃, the hot pressing pressure is 1MPa, and the hot pressing time is 1.5 min/mm.
The pressed plywood from example 3 was tested after 5-7 days at room temperature. The plywood of example 3 had a bond strength as measured by the fast test method for type i panels in GB/T9846-2004, i.e. boiling in boiling water for 3 hours, multiplied by a factor of 0.9, with the results shown in table 1, where the plywood strength was the test result for 14 test pieces, the numerator was the average bond strength, and the denominator was the lowest strength-highest strength; the formaldehyde emission was measured by the dryer method specified in 4.12 of GB/T17657-2013, and the results are shown in Table 1.
Example 4
The invention provides a method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues, which comprises the following steps:
mixing 36g of cellulosic ethanol fermentation residues with 36g of 10 wt% NaOH solution, and stirring at 90 ℃ for 1h to obtain a first activated product;
adding 23g of phenol into the first activated product, and fully reacting for 1h at 100 ℃ to obtain a second activated product;
adding 6.67g of 30 wt% NaOH aqueous solution and 24.11g of 37 wt% formaldehyde aqueous solution into the second activation product, and reacting at 80 ℃ for 1h to obtain a first polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 11.68g of 37 wt% formaldehyde aqueous solution into the first polycondensation product, and reacting at 80 ℃ for 1h to obtain a second polycondensation product;
adding 5.33g of 30 wt% NaOH aqueous solution and 7.68g of 37 wt% formaldehyde aqueous solution into the second polycondensation product, and reacting at 80 ℃ for 1h to obtain a third polycondensation product;
and adding 7.83g of 30 wt% NaOH aqueous solution and 5g of urea into the third polycondensation product, reacting for 0.5h at 70 ℃, cooling and discharging to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
Another embodiment of the invention provides a low-formaldehyde water-resistant copolycondensation resin adhesive prepared by the method of embodiment 4. The low-aldehyde water-resistant copolycondensation resin adhesive of example 4 was measured for solid content, viscosity and pH as specified in GB/T14074-2006, and the results are shown in table 1.
Another embodiment of the present invention provides a poplar three-ply plywood, which is obtained by gluing the low-formaldehyde water-resistant copolycondensation resin adhesive of embodiment 4, wherein the gluing amount of the veneer is 280-316g/m2The hot pressing temperature is 145 ℃, the hot pressing pressure is 1MPa, and the hot pressing time is 1.5 min/mm.
The pressed plywood from example 4 was tested after 5-7 days at room temperature. The plywood of example 4 had a bond strength as measured by the fast test method for type i panels in GB/T9846-2004, i.e. boiling in boiling water for 3 hours, multiplied by a factor of 0.9, with the results shown in table 1, where the plywood strength is the test result for 14 test pieces, the numerator is the average bond strength, and the denominator is the lowest strength-highest strength; the formaldehyde emission was measured by the dryer method specified in 4.12 of GB/T17657-2013, and the results are shown in Table 1.
Table 1 examples 1-4 low-formaldehyde water-resistant copolycondensation resin adhesive properties and plywood properties prepared
Figure BDA0001717702470000091
As can be seen from the data in Table 1, the plywood obtained in examples 1-4 has boiling water resistance and strength meeting the class I board (0.7 MPa or more) standard specified in GB/T9846-2004, and has formaldehyde emission reaching E0The limited requirement of the grade (less than or equal to 0.5mg/L) is met, and the low-aldehyde water-resistant copolycondensation resin adhesive in the examples 1-4 can be used as a low-cost, low-aldehyde and high-performance artificial board adhesive.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (8)

1. A method for preparing a low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues is characterized by comprising the following steps:
mixing the cellulosic ethanol fermentation residues with a first alkali solution, and activating to obtain a first activated product; the first alkali solution is sodium hydroxide alkali solution, and the mass concentration of the first alkali solution is 5-10%; the weight ratio of the cellulosic ethanol fermentation residues to the first alkali solution is 1: 0.8-1.5; the activation temperature is 85-100 ℃, and the activation time is 0.5-1 h;
carrying out a first reaction on the first activation product and phenol to obtain a second activation product; the weight ratio of the phenol to the cellulosic ethanol fermentation residues is 0.67-9: 1;
carrying out a second reaction on the second activation product, a second alkali solution and a first formaldehyde solution to obtain a first polycondensation product;
carrying out a third reaction on the first polycondensation product, a third alkali solution and a second formaldehyde solution to obtain a second polycondensation product;
carrying out a fourth reaction on the second polycondensation product, a fourth alkali solution and a third furfural solution to obtain a third polycondensation product;
and carrying out a fifth reaction on the third polycondensation product, a fifth alkali solution and urea, and cooling to obtain the low-formaldehyde water-resistant copolycondensation resin adhesive.
2. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the temperature of the first reaction is 90-100 ℃ and the reaction time is 1-2 h.
3. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive by using the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the addition amount of the second alkali solution is 10-15% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the first formaldehyde solution is 25-35% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the second reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
4. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the addition amount of the third alkali solution is 5-10% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the second formaldehyde solution is 20-25% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the third reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
5. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive by using the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the addition amount of the fourth alkali solution is 5-10% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the addition amount of the third furfural solution is 15-20% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the fourth reaction is 80-90 ℃, and the reaction time is 0.5-1 h.
6. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive by using the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the addition amount of the fifth alkali solution is 10-15% of the sum of the mass of the phenol and the cellulosic ethanol fermentation residues;
the adding amount of the urea is 3-8% of the mass sum of the phenol and the cellulosic ethanol fermentation residues;
the temperature of the fifth reaction is 60-70 ℃, and the reaction time is 0.3-0.6 h.
7. The method for preparing the low-aldehyde water-resistant copolycondensation resin adhesive from the cellulosic ethanol fermentation residues as claimed in claim 1, wherein the second alkali solution is sodium hydroxide alkali solution, and the mass concentration is 20-40%;
the third alkali solution is sodium hydroxide alkali solution, and the mass concentration of the third alkali solution is 20-40%;
the fourth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fourth alkali solution is 20-40%;
the fifth alkali solution is sodium hydroxide alkali solution, and the mass concentration of the fifth alkali solution is 20-40%;
the mass concentration of the formaldehyde solution is 30-50%.
8. A low-aldehyde water-resistant copolycondensation resin adhesive prepared by the method of any one of claims 1 to 7.
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