CN113088222B - Adhesive for preventing plate from warping and preparation method thereof - Google Patents
Adhesive for preventing plate from warping and preparation method thereof Download PDFInfo
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- CN113088222B CN113088222B CN202110480552.7A CN202110480552A CN113088222B CN 113088222 B CN113088222 B CN 113088222B CN 202110480552 A CN202110480552 A CN 202110480552A CN 113088222 B CN113088222 B CN 113088222B
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an adhesive for preventing a plate from warping, which comprises the following raw materials in parts by weight: 90-110 parts of corn starch, 30-40 parts of hydrogen peroxide, 10-20 parts of erucamide, 10-20 parts of hydroxymethyl acrylamide, 0.03-0.05 part of sodium bisulfite, 0.4-0.7 part of amine trimethylene sodium phosphate and 0.1-0.3 part of glycerol monooleate; the invention also discloses a preparation method of the adhesive for preventing the plate from warping, which comprises the following steps: mixing, oxidizing, stirring, grafting, crosslinking, sealing, and fully reacting to obtain the adhesive. The adhesive sheet prepared by the invention can be used for a long time, is anti-warping, free of formaldehyde release and prevention, safe and environment-friendly.
Description
[ technical field ] A
The invention belongs to the technical field of plate warping prevention, and particularly relates to an adhesive for preventing plate warping and a preparation method thereof.
[ background of the invention ]
The plywood is one of common furniture materials and is one of three artificial boards. In order to improve the anisotropic characteristics of natural wood as much as possible, the plywood has uniform characteristics and stable shape, and mainly solves the problems of high price and high wood source consumption of solid wood boards. Plywood is generally a three-layer or multi-layer plate-shaped material formed by rotationally cutting wood sections into veneers or slicing battens into thin wood and gluing the veneers by using an adhesive, and is usually formed by gluing odd single-layer plates and mutually vertical fiber directions of the veneers of adjacent layers.
The adhesive is a substance with good adhesive property, is adhered on the surface through adhesive force and cohesive force to play a role of connecting objects, and is prepared in the common plywood. Most of the prior adhesives in China are urea-formaldehyde resin, modified urea-formaldehyde resin and amino resin, but when the adhesives are used, a large amount of free formaldehyde can be generated, and the free formaldehyde can be still released and prevented in the use process of the plywood, so that the health of people is seriously influenced, and because of the properties of the adhesives, the brittleness and cracking possibility of the board can be increased due to the existence of internal stress in the curing process; but when the dosage of the adhesive is less, the problems of incomplete adhesion, degumming and the like of the plates due to insufficient adsorption force can also occur.
Meanwhile, the adhesive with high performance and low price becomes a popular object of current research, the renewable natural polymer raw material can be used as a cost performance material for manufacturing sticky materials, and the corn starch becomes a finally selected raw material, so that the adhesive is low in price, renewable and environment-friendly. However, in the current research, the adhesive of corn starch is the same as the traditional phenolic resin adhesive, and cannot prevent the water absorption of wood, and simultaneously cannot prevent the warping caused by unbalanced inward shrinkage and outward expansion degrees of the wood due to the water absorption. The board will warp after a period of use.
[ summary of the invention ]
The invention aims to provide an adhesive for preventing a plate from warping and a preparation method thereof, and aims to solve the problems that the conventional plate adhesive is not enough in hardness and waterproof, absorbs water to cause the plate to warp and the like; the adhesive disclosed by the invention has stronger waterproof performance, and a plate prepared by using the adhesive disclosed by the invention can be used for a long time, is warped, free from formaldehyde release and prevention, safe, green and environment-friendly.
In order to solve the technical problem, the invention adopts the following technical scheme:
the adhesive for preventing the warping of the plate comprises the following raw materials in parts by weight: 90-110 parts of corn starch, 30-40 parts of hydrogen peroxide, 10-20 parts of erucamide, 10-20 parts of hydroxymethyl acrylamide, 0.03-0.05 part of sodium bisulfite, 0.4-0.7 part of amine trimethylene sodium phosphate and 0.1-0.3 part of glycerol monooleate.
A preparation method of an adhesive for preventing a plate from warping comprises the following steps:
s1: weighing the raw materials according to the weight ratio, and weighing a certain weight of water for later use;
s2: adding the weighed corn starch into water, uniformly stirring until a pasty starch solution is obtained, adding hydrogen peroxide into the solution for oxidation, and adjusting the pH value.
S3: erucamide and hydroxymethyl acrylamide are dissolved in water, slowly added into the oxidized starch solution, continuously stirred in the process, and added with amine trimethylene sodium phosphate;
s4: adding sodium bisulfite solution, controlling the temperature, slowly adding the solution, and finishing the reaction when the solution is viscous; and adding glycerol monooleate into the solution after the reaction is finished, adjusting the pH value in the process, and stirring to obtain the adhesive.
Further, the weight of water in S1 is 1.2-1.5 times of the weight of starch.
Further, the oxidation time in S2 is 4-6 h.
Furthermore, after adding hydrogen peroxide into S2, the temperature needs to be controlled at 40-55 ℃, and the pH value needs to be controlled at 6.5-8.
Furthermore, the S3 needs to react for 0.5-1h after adding the solution of erucamide and hydroxymethyl acrylamide, and reacts for 0.1-0.3h after adding the sodium trimetaphosphate.
Furthermore, the temperature needs to be controlled at 10-15 ℃ in the process of adding the sodium bisulfite into the S4.
Further, the addition of sodium bisulfite to S4 requires a reaction time of 1-2 hours.
Further, the pH value is adjusted to 6-9 in S4.
Further, in S4, after the system is creamy yellow and stable, discharging and adjusting the pH value to be neutral to prepare the adhesive.
The invention has the following beneficial effects:
(1) the method comprises the following steps of firstly, carrying out oxidation treatment on corn starch to oxidize hydroxyl in a starch solution into carbonyl and carboxyl with stronger activity, wherein hydrogen bonds formed by the carbonyl and the carboxyl are less prone to damage and can be enhanced; the weak oxidation performance of hydrogen peroxide is utilized, long-time continuous oxidation is carried out, the phenomena of starch solution coagulation and agglomeration caused by too high oxidation rate, viscosity reduction and material waste caused by the phenomenon of viscosity reduction are avoided, the pH value is adjusted to be alkaline, and the condensation polymerization phenomenon caused by strong carboxyl activity in the oxidation process is prevented;
(2) according to the adhesive, erucamide and hydroxymethyl acrylamide are used for grafting, the erucamide is high-temperature resistant, is not easy to turn yellow, and has better property than oleamide, and meanwhile, hydroxymethyl acrylamide molecules have double bonds conjugated with carbonyl groups and hydroxymethyl groups with high reaction activity, so that the grafting reaction time can be reduced, and the grafting completion degree is improved; meanwhile, the waterproof performance of the adhesive is indirectly improved, and the adhesive can be used for a long time even in a humid environment;
(3) the sodium bisulfite is used as the sealant, the sealing effect is better than that of diisocyanamide, the adhesive using the sodium bisulfite as the sealant has higher viscosity, and the amine trimethylene sodium phosphate and the polyol fatty acid are used as the curing agent and the emulsifier, so that the adhesive can be promoted to permeate into a bonded object, the hardness is improved, and when the adhesive is used in a plate, the hardness of the plate can be enhanced, and the adhesive is not easy to degum;
(4) the adhesive disclosed by the invention has higher waterproof performance, the defect of poor waterproof performance of the traditional corn starch adhesive is overcome, the water absorption of the plate can be reduced, the water absorption of the plate is reduced, the water balance in the plate is maintained, the plate warping problem caused by inconsistent water absorption expansion and water loss shrinkage degrees of the plate is solved, and the plate can be used for a long time without warping.
[ detailed description ] embodiments
For a better understanding of the present invention, the invention is further explained below in conjunction with specific embodiments, it should be emphasized that the following is merely exemplary and is not intended to limit the scope of the invention and its applications, and any equivalent changes or substitutions made on this basis fall within the scope of the invention.
Example 1
The adhesive for preventing the plate from warping comprises the following raw materials in parts by weight: 110 parts of corn starch, 30 parts of hydrogen peroxide, 20 parts of erucamide, 10 parts of hydroxymethyl acrylamide, 0.05 part of sodium bisulfite, 0.4 part of sodium amine trimethophor phosphate and 0.3 part of glycerol monooleate.
A preparation method of an adhesive for preventing a plate from warping comprises the following steps:
s1: weighing the raw materials according to the weight ratio, and weighing a certain weight of water for later use;
s2: adding the weighed corn starch into water with the weight 1.2 times of that of the corn starch, uniformly stirring until a pasty starch solution is obtained, adding hydrogen peroxide into the solution for oxidation, controlling the temperature to be 55 ℃, adjusting the pH value to be 6.5, and continuously reacting for 4 hours.
S3: dissolving erucamide and hydroxymethyl acrylamide in water, slowly adding into the oxidized starch solution, continuously stirring during the process, continuously reacting for 1h, and adding sodium trimethoprim phosphate to continuously react for 0.1 h;
s4: adding sodium bisulfite solution, controlling the temperature to be reduced to 15 ℃, slowly adding the sodium bisulfite solution, and finishing the reaction when the solution is viscous; and adding glycerol monooleate into the solution after the reaction is finished, adjusting the pH value to be 6 in the process, and after the stirring is finished and the system is stable in cream yellow color, adjusting the pH value to be neutral to prepare the adhesive.
Example 2
The adhesive for preventing the warping of the plate comprises the following raw materials in parts by weight: 90 parts of corn starch, 40 parts of hydrogen peroxide, 10 parts of erucamide, 20 parts of hydroxymethyl acrylamide, 0.03 part of sodium bisulfite, 0.7 part of sodium amine trimethylene phosphate and 0.1 part of glycerol monooleate.
The preparation method of the adhesive for preventing the plate from warping comprises the following steps:
s1: weighing the raw materials according to the weight ratio, and weighing a certain weight of water for later use;
s2: adding the weighed corn starch into water with the weight 1.5 times of that of the corn starch, uniformly stirring until a pasty starch solution is obtained, adding hydrogen peroxide into the solution for oxidation, controlling the temperature to be 40 ℃, adjusting the pH value to be 8, and continuously reacting for 6 hours.
S3: dissolving erucamide and hydroxymethyl acrylamide in water, slowly adding into the oxidized starch solution, continuously stirring during the process, continuously reacting for 0.5h, and adding into sodium trimetaphosphate to continuously react for 0.3 h;
s4: adding sodium bisulfite solution, controlling the temperature to be reduced to 10 ℃, slowly adding the sodium bisulfite solution, and finishing the reaction when the solution is viscous; and (3) adding glycerol monooleate into the solution after the reaction is finished, adjusting the pH value to 9 in the process, and after the stirring is finished and the system is creamy yellow and stable, adjusting the pH value to be neutral to prepare the adhesive.
Example 3
The adhesive for preventing the warping of the plate comprises the following raw materials in parts by weight: 90-110 parts of corn starch, 35 parts of hydrogen peroxide, 15 parts of erucamide, 14 parts of hydroxymethyl acrylamide, 0.04 part of sodium bisulfite, 0.5 part of amine trimethylene sodium phosphate and 0.2 part of glycerol monooleate.
A preparation method of an adhesive for preventing a plate from warping comprises the following steps:
s1: weighing the raw materials according to the weight ratio, and weighing a certain weight of water for later use;
s2: adding the weighed corn starch into water with the weight 1.3 times of that of the corn starch, uniformly stirring until pasty starch solution is obtained, adding hydrogen peroxide into the solution for oxidation, controlling the temperature to be 50 ℃, adjusting the pH value to be 7, and continuously reacting for 5 hours.
S3: dissolving erucamide and hydroxymethyl acrylamide in water, slowly adding into the oxidized starch solution, continuously stirring during the process, continuously reacting for 1h, and adding sodium trimethoprim phosphate to continuously react for 0.2 h;
s4: adding sodium bisulfite solution, controlling the temperature to be reduced to 10 ℃, slowly adding the sodium bisulfite solution, and finishing the reaction when the solution is viscous; and adding glycerol monooleate into the solution after the reaction is finished, adjusting the pH value to be 8 in the process, and after the stirring is finished and the system is stable in cream yellow color, adjusting the pH value to be neutral to prepare the adhesive.
Comparative example 1
The experimental procedure was essentially the same as in example 3, except that no sodium aminomethylene phosphate was added to the starting materials.
Comparative example 2
The experimental procedure was essentially the same as in example 3, except that glycerol monooleate was not present in the feed.
Comparative example 3
The experimental procedure was substantially the same as in example 3, except that the sodium trimetaphosphate and glyceryl monooleate were not added to the starting materials,
examples of the experiments
The above examples 1 to 3 and comparative examples 1 to 3 were used to prepare a multi-ply plywood
The experimental panel and the middle filler are all eucalyptus, the experimental multilayer board is provided with 5 layers and respectively comprises a middle-two-layer outer layer, a three-layer middle layer and a middle filler, the plywood is subjected to two processes of cold pressing and hot pressing to prepare plywood with the thickness of 1.5cm, various indexes such as the 24-hour water absorption thickness expansion rate of the prepared plywood are detected, 3 boards in each group are taken for detection in the experiment, and the average value is taken to obtain the result shown in the following table 1:
TABLE 1 mean values of tests on plywood produced in examples 1-3 and comparative examples 1-3
The data in table 1 show that no formaldehyde release is generated in any of the examples or comparative examples, which is due to the advantages of the adhesive prepared from pure natural renewable materials, such as no formaldehyde, safety and environmental protection; while the bonding strength at 110 ℃ in example 1 and example 2 is 0.72MPa and 0.71MPa, respectively, in the most preferred example, the bonding strength at 110 ℃ in example 3 is as high as 0.75MPa, while the bonding strength under the same conditions in comparative example 1 is only 0.66MPa, and in comparative example 2 is 0.63MPa, which are respectively 0.09MPa and 0.12MPa lower than those in example 3, and in comparative example 3, the bonding strength under the same conditions is only 0.51MPa and 0.24MPa lower than that in example 3 due to the lack of both sodium aminotrimethylene phosphate and glycerol monooleate, we can see, according to the data, that 0.09+0.12 ═ 0.21 < 0.24, and that the synergistic effect of the sodium aminotrimethylene phosphate and glycerol monooleate in the raw materials is increased by 14.3 ÷ (0.24-0.21) ÷ 14.3%; the sum of the independent action effect values of the amine sodium trimethoprim phosphate and the glycerol monooleate in the adhesive is smaller than that of the adhesive prepared by simultaneously using the two raw materials, which is probably that the amine sodium trimethoprim phosphate can have the effect of curing the adhesive, and the synergistic action is generated when the emulsifier glycerol monooleate is added, so that the bonding strength of the adhesive under the same condition can be synergistically improved. Similarly, we can calculate the result according to the water absorption thickness expansion rate of 24h in the table. The waterproof property of the adhesive is improved, the situation that the boards are warped does not occur in examples 1-3 and comparative examples 1-2 in the situation that the boards are warped for 3 months, and the adhesive is proved to be capable of effectively reducing the water absorption degree of the plywood, and improving the problem of board warping caused by unbalanced water absorption expansion and contraction of the plywood.
The above description should not be taken as limiting the invention to the particular embodiments described, but rather as enabling the person skilled in the art to make several simple deductions or substitutions without departing from the spirit of the invention, it should be understood that the invention is defined by the claims as filed.
Claims (10)
1. The adhesive for preventing the board from warping is characterized by comprising the following raw materials in parts by weight: 90-110 parts of corn starch, 30-40 parts of hydrogen peroxide, 10-20 parts of erucamide, 10-20 parts of hydroxymethyl acrylamide, 0.03-0.05 part of sodium bisulfite, 0.4-0.7 part of amine trimethylene sodium phosphate and 0.1-0.3 part of glycerol monooleate.
2. The preparation method of the plate warping-preventing adhesive according to claim 1, characterized by comprising the following steps:
s1: weighing the raw materials according to the weight ratio, and weighing a certain weight of water for later use;
s2: adding the weighed corn starch into water, uniformly stirring until a pasty starch solution is obtained, adding hydrogen peroxide into the solution for oxidation, and adjusting the pH value;
s3: erucamide and hydroxymethyl acrylamide are dissolved in water, slowly added into the oxidized starch solution, continuously stirred in the process, and added with amine trimethylene sodium phosphate;
s4: adding sodium bisulfite solution, controlling the temperature, slowly adding the solution, and finishing the reaction when the solution is viscous; and (3) adding glycerol monooleate into the solution after the reaction is finished, adjusting the pH value in the process, and stirring to obtain the adhesive.
3. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the weight of water in S1 is 1.2-1.5 times of the weight of starch.
4. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the oxidation time in S2 is 4-6 h.
5. The preparation method of the adhesive for preventing the warping of the board, according to claim 2, is characterized in that after hydrogen peroxide is added into S2, the temperature is controlled to be 40-55 ℃, and the pH value is controlled to be 6.5-8.
6. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the S3 is added with a solution of erucamide and methylolacrylamide and then reacted for 0.5-1h, and the S3 is added with sodium trimetaphosphate and then reacted for 0.1-0.3 h.
7. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the temperature is controlled to be 10-15 ℃ in the process of adding sodium bisulfite into S4.
8. The preparation method of the adhesive for preventing the warping of the board according to claim 2, wherein sodium bisulfite is added into S4 for reaction for 1-2 h.
9. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the pH value is adjusted to 6-9 in S4.
10. The preparation method of the adhesive for preventing the warping of the board as claimed in claim 2, wherein the adhesive is prepared by discharging and adjusting the pH to be neutral after the system is stable in creamy yellow color in S4.
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