CN109467697B - Branched polyamide-glyoxal resin adhesive, preparation method and application - Google Patents
Branched polyamide-glyoxal resin adhesive, preparation method and application Download PDFInfo
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- CN109467697B CN109467697B CN201811307822.9A CN201811307822A CN109467697B CN 109467697 B CN109467697 B CN 109467697B CN 201811307822 A CN201811307822 A CN 201811307822A CN 109467697 B CN109467697 B CN 109467697B
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
- C08G69/50—Polymers modified by chemical after-treatment with aldehydes
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
Abstract
The invention discloses a branched polyamide-glyoxal resin adhesive which is prepared by carrying out addition and condensation reaction on branched polyamide and glyoxal, wherein the branched polyamide-glyoxal resin adhesive is prepared by carrying out deamination condensation reaction on tri (2-aminoethyl) amine and urea under the conditions of no solvent and no catalyst, and the branched polyamide-glyoxal resin adhesive is wine red uniform liquid, has the solid content of 55-60%, has the pH of 7.0-8.0 and has the storage period of more than 60 days. The adhesive has the characteristics of no formaldehyde release, good storage stability and excellent performance, and the overall performance of the adhesive is greatly improved. The invention also provides a preparation method of the adhesive.
Description
Technical Field
The invention relates to the technical field of wood processing production, in particular to a branched polyamide-glyoxal resin adhesive, a preparation method and application thereof.
Background
Urea-formaldehyde resin (UF), phenol-formaldehyde resin (PF) and melamine formaldehyde resin (MF) are traditional resin adhesives widely used in the production of artificial boards at present. The three resins are all prepared by the addition and polycondensation reaction of formaldehyde, urea, phenol and melamine. Because formaldehyde is a main synthetic raw material, more or less unreacted formaldehyde, namely free formaldehyde, remains in the final resin; in addition, since both the addition and polycondensation reactions are reversible reactions, resin molecules are depolymerized particularly under high temperature and high humidity conditions. Both of the two reasons can cause the artificial board product to gradually release formaldehyde in the using process, thereby causing harm to human bodies and environment. With the social progress and the enhancement of environmental awareness, the problem of formaldehyde emission is increasingly highlighted, and the application of formaldehyde-based resins is facing unprecedented challenges.
Of the three resins, urea-formaldehyde resin has the remarkable advantages of low cost, excellent performance and easy large-scale industrial production and use, so that the urea-formaldehyde resin is widely used for producing shaving boards, plywood and medium-density county fiberboards. However, the urea-formaldehyde resin also has the defects of poor durability of the glued product and large formaldehyde emission. In order to reduce the formaldehyde emission of urea-formaldehyde resin glued products, low-molar-ratio synthesis technology is generally adopted, for example, the molar ratio of urea to formaldehyde is close to 1:1 in the process of manufacturing particle boards. The low molar ratio urea-formaldehyde resin, while significantly reducing formaldehyde emissions, also results in a substantial reduction in the overall performance of the panel. Meanwhile, because the urea-formaldehyde resin structure has instable groups such as methylene ether bond or hydroxymethyl, the urea-formaldehyde resin adhesive product can continuously release formaldehyde in the application period, thereby forming long-term potential threat to the environment and human health. The pursuit of zero or ultra-low formaldehyde emission has prompted the academic circles and the industrial circles of all countries in the world to actively find novel formaldehyde-free resins with low cost, excellent performance and simple production process.
Isocyanate adhesive (pMDI) is the most important non-formaldehyde series artificial board adhesive at present, has already realized commercial process and application at home and abroad, about 20% of oriented strand boards in North America use the isocyanate adhesive, China also has a considerable number of production lines to use, but its cost is about ten times of UF resin, because use the release agent, etc. at the same time, the application process is relatively complicated, the market share is still very limited at present. The biomass wood adhesive represented by tannin, soy protein, lignin and the like has also been applied to industrial production, but is difficult to meet the industrial large-scale industrial use requirements of the artificial board industry due to various reasons such as total amount of raw materials, cost, complex application process and the like.
The solution of balancing cost and performance is possible to realize by taking urea as a main raw material and finding a formaldehyde substitute. Among them, the research of using glyoxal to replace formaldehyde to prepare wood adhesives has attracted the attention of some domestic and foreign scholars. The literature "Performance and reaction mechanism of zero for urea-formaldehyde-injection urea-gyoxal (ug) resin" reports the synthesis principle of a urea-glyoxal wood adhesive; the patent ZL201310274163.4 discloses a preparation method of a resin adhesive without formaldehyde release, which directly takes urea and glyoxal as synthetic raw materials, is prepared by step-by-step synthesis and has certain bonding performance. However, the reaction of urea and glyoxal under acidic or basic conditions easily generates a dihydroxyvinyl urea cyclic structure, which results in the consumption of functional groups, and the polymer has a low molecular weight and a low degree of branching. Meanwhile, the polycondensation reaction generates hemiacetal and linear ether bond structures, resulting in poor stability of the main structure of the resin. Therefore, the bonding strength of the resin directly synthesized by urea and glyoxal is not ideal, and especially the water resistance of the artificial board is poor.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a branched polyamide-glyoxal resin adhesive which has the characteristics of no formaldehyde release, good storage stability and excellent performance, and realizes the great improvement of the overall performance of the adhesive, and the technical scheme adopted by the invention is as follows:
the branched polyamide-glyoxal resin adhesive is prepared by addition and condensation reaction of branched polyamide and glyoxal, wherein the branched polyamide-glyoxal resin adhesive is prepared by deamination condensation reaction of tri (2-aminoethyl) amine and urea under the conditions of no solvent and no catalyst, and the branched polyamide-glyoxal resin adhesive is wine red uniform liquid, has the solid content of 55-60%, has the pH of 7.0-8.0 and has the storage period of more than 60 days.
Further, the branched polyamide molecular branch has-CH2-CH2-NHCONH-repeat structure and branched chain end-CH2-CH2-NH-CO-NH2And (5) structure.
The invention also provides a preparation method of the branched polyamide-glyoxal resin adhesive, which comprises the following steps:
a. the initial stage of the reaction will be measured as T1Heating the tri (2-aminoethyl) amine to 40-60 ℃ in an oil bath, adding the measured U under stirring1Urea of (a), the molar ratio U of urea to tris (2-aminoethyl) amine1/T1Controlling the temperature to be between 3.5 and 5.0; continuously heating to 110-;
b. adding a second amount of T after the reaction is carried out for 2.0 to 3.0 hours at the temperature of 110-2Tri (2-aminoethyl) amine of (A) to (B) to (U)1/(T1+T2) The molar ratio is 0.7-1.0, the reaction is carried out at the temperature of 3.0Adding urea for the second time after 4.0 hours, and metering the amount of the urea to be U2Make (U)1+U2)/(T1+T2) The molar ratio is 2.0-2.6, the heat preservation is carried out for 1.5-2.0 hours, and the materials are discharged and cooled;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a 40% (mass fraction w%) glyoxal solution metered as G to 8.0-9.0 at room temperature, heating the glyoxal solution to about 40 ℃ in a water bath, adding metered tris (2-aminoethyl) amine-urea polyamide solids while stirring in an amount calculated based on the urea used for the synthesized tris (2-aminoethyl) amine-urea polyamide to achieve a glyoxal/urea molar ratio of 0.8-1.2; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, and adjusting the pH value to 7.0-8.0 after natural cooling to obtain the branched polyamide-glyoxal resin adhesive.
The branched polyamide-glyoxal resin adhesive is applied to the industrial production of artificial boards.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polyamide polymer with a branched chain structure is prepared by utilizing the deamination condensation reaction of the tri (2-aminoethyl) amine and the urea, and the polyamide polymer is further reacted with the glyoxal to prepare the polyamide-glyoxal resin adhesive by utilizing the characteristics of high stability, good water solubility and urea reaction activity.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present application, the present invention will be further described with reference to the following examples, which include, but are not limited to, the following examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The branched polyamide-glyoxal resin adhesive is prepared by carrying out addition and condensation reaction on branched polyamide prepared by deamination condensation reaction of tri (2-aminoethyl) amine and urea under the conditions of no solvent and no catalyst and is wine red uniform liquid, wherein the solid content of the liquid is 55-60%, the pH value of the liquid is 7.0-8.0, and the storage period of the liquid is more than 60 days. Wherein the branched polyamide molecular branch has-CH2-CH2-NHCONH-repeat structure and chain end-CH2-CH2-NH-CO-NH2And (5) structure. The branched polyamide-glyoxal resin adhesive is applied to the industrial production of artificial boards.
The preparation method of the branched polyamide-glyoxal resin adhesive comprises the following steps:
a. the initial stage of the reaction will be measured as T1Heating the tri (2-aminoethyl) amine to 40-60 ℃ in an oil bath, adding the measured U under stirring1Urea of (a), the molar ratio U of urea to tris (2-aminoethyl) amine1/T1Controlling the temperature to be between 3.5 and 5.0; continuously heating to 110-;
b. adding a second amount of T after the reaction is carried out for 2.0 to 3.0 hours at the temperature of 110-2Tri (2-aminoethyl) amine of (A) to (B) to (U)1/(T1+T2) The molar ratio is 0.7-1.0, the second urea is added after the heat preservation reaction is carried out for 3.0-4.0 hours, and the metered amount is U2Make (U)1+U2)/(T1+T2) The molar ratio is 2.0-2.6, the heat preservation is carried out for 1.5-2.0 hours, and the materials are discharged and cooled;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a 40% (mass fraction) glyoxal solution which is measured as G to 8.0-9.0 at room temperature, heating the mixture to about 40 ℃ in a water bath, adding measured tris (2-aminoethyl) amine-urea polyamide solid according to the amount of urea used for synthesizing the tris (2-aminoethyl) amine-urea polyamide under stirring to ensure that the molar ratio of glyoxal/urea is 0.8-1.2; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, and adjusting the pH value to 7.0-8.0 after natural cooling to obtain the branched polyamide-glyoxal resin adhesive.
The preparation process of the adhesive does not use formaldehyde, so that no formaldehyde is released, the prepared adhesive has no obvious change in appearance (color and viscosity) after being placed at room temperature for 60 days, and the storage stability is high.
According to different hot pressing temperatures in the plywood pressing process, the water resistance of the plywood is different: (1) when the hot pressing temperature is 160-180 ℃ and the hot pressing time is 5 minutes, according to the test of national standard GB/T17657 plus 2013 test method for physical and chemical properties of artificial boards and decorative artificial boards, the wet bonding strength of a test piece after being soaked in cold water at a temperature of not less than 17 ℃ for 24 hours is more than 0.7Mpa, and the water resistance requirement of the national standard GB/T98684 plus 2015 common plywood on the III type plywood can be met; (2) the hot pressing temperature is 190-220 ℃, the hot pressing time is 5 minutes, the bonding strength of the test piece after being soaked in hot water at 63 ℃ for 3 hours is more than 0.7Mpa, and the water resistance requirement of the national standard GB/T98684 plus materials 2015 common plywood on the class II plywood can be met.
The preparation method adopts conventional equipment, and the preparation examples are as follows:
example 1:
the method is synthesized by taking tri (2-aminoethyl) amine, urea and glyoxal as raw materials, wherein:
a. the initial stage of the reaction will be measured as T1Heating the tri (2-aminoethyl) amine to 40-60 ℃ in an oil bath, adding the measured U under stirring1Urea of (a), the molar ratio U of urea to tris (2-aminoethyl) amine1/T1Controlling the temperature to be about 3.5; continuously heating to 110 ℃, carrying out heat preservation reaction, and absorbing overflowed ammonia gas by using an ammonia gas absorption device in the reaction process;
b. after the reaction is carried out for 3.0 hours at 110 ℃, a second dosage of T is added2Tri (2-aminoethyl) amine of (A) to (B) to (U)1/(T1+T2) The molar ratio is 0.70, the second urea is added after the heat preservation reaction is carried out for 3.0 to 4.0 hours, and the calculation is carried outAmount is U2Make (U)1+U2)/(T1+T2) The molar ratio is 2.0, the heat preservation is carried out for 1.5 to 2.0 hours, and the materials are discharged and cooled;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a 40% (mass fraction w%) glyoxal solution metered as G to 8.0-9.0 at room temperature, heating the glyoxal solution to about 40 ℃ in a water bath, adding metered tris (2-aminoethyl) amine-urea polyamide solid while stirring, wherein the molar ratio of glyoxal/urea is 0.8, and the measured tris (2-aminoethyl) amine-urea polyamide solid is calculated according to the urea used for synthesizing the tris (2-aminoethyl) amine-urea polyamide; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, naturally cooling, and adjusting the pH value to 7.0-8.0 to obtain the final branched polyamide-glyoxal resin adhesive.
Example 2:
the method is synthesized by taking tri (2-aminoethyl) amine, urea and glyoxal as raw materials, wherein:
a. the initial stage of the reaction will be measured as T1Heating the tri (2-aminoethyl) amine to 40-60 ℃ in an oil bath, adding the measured U under stirring1Urea of (a), the molar ratio U of urea to tris (2-aminoethyl) amine1/T1Controlling the temperature to be about 4.0; continuously heating to 115 ℃, carrying out heat preservation reaction, and absorbing overflowed ammonia gas by using an ammonia gas absorption device in the reaction process;
b. after 2.5 hours of reaction at 115 ℃ a second quantity T is added2Tri (2-aminoethyl) amine of (A) to (B) to (U)1/(T1+T2) The molar ratio is 0.85, and the second urea (U) is added after the reaction is carried out for 3.0 to 4.0 hours under the condition of heat preservation2) Make (U)1+U2)/(T1+T2) The molar ratio is 2.3, the heat preservation is carried out for 1.5 to 2.0 hours, and the materials are discharged and cooled;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a 40% (mass fraction w%) glyoxal solution which is measured as G to 8.0-9.0 at room temperature, heating the glyoxal solution to about 40 ℃ in a water bath, adding measured tris (2-aminoethyl) amine-urea polyamide solid while stirring according to the amount of urea used for synthesizing tris (2-aminoethyl) amine-urea polyamide so that the molar ratio of glyoxal/urea is 1.0; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, naturally cooling, and adjusting the pH value to 7.0-8.0 to obtain the final branched polyamide-glyoxal resin adhesive.
Example 3:
the method is synthesized by taking tri (2-aminoethyl) amine, urea and glyoxal as raw materials, wherein:
a. the initial stage of the reaction will be measured as T1Heating the tri (2-aminoethyl) amine to 40-60 ℃ in an oil bath, adding the measured U under stirring1Urea of (a), the molar ratio U of urea to tris (2-aminoethyl) amine1/T1Controlling the temperature to be about 5.0; continuously heating to 120 ℃, keeping the temperature for reaction, and absorbing overflowing ammonia gas by an ammonia gas absorption device in the reaction process;
b. after the reaction is carried out for 2.0 hours at the temperature of 120 ℃, a second dosage of T is added2Tri (2-aminoethyl) amine of (A) to (B) to (U)1/(T1+T2) The molar ratio is 1.0, and the second urea (U) is added after the reaction is carried out for 3.0 to 4.0 hours under the condition of heat preservation2) Make (U)1+U2)/(T1+T2) The molar ratio is 2.6, the heat preservation is carried out for 1.5 to 2.0 hours, and the materials are discharged and cooled;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a 40% (mass fraction w%) glyoxal solution which is measured as G to 8.0-9.0 at room temperature, heating the glyoxal solution to about 40 ℃ in a water bath, adding measured tris (2-aminoethyl) amine-urea polyamide solid while stirring according to the amount of urea used for synthesizing tris (2-aminoethyl) amine-urea polyamide so that the molar ratio of glyoxal/urea is 1.2; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, naturally cooling, and adjusting the pH value to 7.0-8.0 to obtain the final branched polyamide-glyoxal resin adhesive.
The adhesives prepared in the embodiments 1-3 are respectively taken, poplar veneers with the thickness of 2mm are used for pressing three-layer plywood, the physical and mechanical properties of the board are tested according to the national standard GB/T17657 plus 2013 physicochemical property test method for artificial boards and decorative artificial boards, and the water resistance of the board is mainly tested. The specific results are as follows:
the hot pressing temperature is 160-180 ℃, the hot pressing time is 5 minutes, and the wet bonding strength of the test piece after being soaked in cold water at 20 ℃ for 24 hours is 0.7-0.85 Mpa; the hot pressing temperature is 190-220 ℃, the hot pressing time is 5 minutes, and the bonding strength of the test piece after being soaked in hot water at 63 ℃ for 3 hours is 0.7-0.95 Mpa.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the scope of the present invention, but all the modifications made by the principles of the present invention and the non-inventive efforts based on the above-mentioned embodiments shall fall within the scope of the present invention.
Claims (2)
1. A preparation method of a branched polyamide-glyoxal resin adhesive is characterized by comprising the following steps: the branched polyamide-glyoxal resin adhesive is prepared by addition and condensation reaction of branched polyamide and glyoxal, wherein the branched polyamide is prepared by deamination condensation reaction of tri (2-aminoethyl) amine and urea under the conditions of no solvent and no catalyst, and the branched polyamide-glyoxal resin adhesive is wine red uniform liquid, has the solid content of 55-60%, has the pH of 7.0-8.0 and has the storage period of more than 60 days;
the branched polyamide has a molecular branch of-CH2-CH2-NHCONH-repeat structure and branched chain end-CH2-CH2-NH-CO-NH2Structure;
the preparation method of the branched polyamide-glyoxal resin adhesive comprises the following steps:
a. in the initial stage of the reaction, heating tri (2-aminoethyl) amine metered as T1 to 40-60 ℃ in an oil bath, adding urea metered as U1 while stirring, and controlling the molar ratio of the urea to the tri (2-aminoethyl) amine as U1/T1 to be 3.5-5.0; continuously heating to 110-;
b. carrying out heat preservation reaction at the temperature of 110-120 ℃ for 2.0-3.0 hours, adding the tri (2-aminoethyl) amine with the dosage of T2 for the second time to ensure that the molar ratio of U1/(T1+ T2) is 0.7-1.0, carrying out heat preservation reaction for 3.0-4.0 hours, adding the urea with the dosage of U2 to ensure that the molar ratio of (U1+ U2)/(T1+ T2) is 2.0-2.6, carrying out heat preservation for 1.5-2.0 hours, discharging and cooling;
c. the cooled product is a tris (2-aminoethyl) amine-urea polyamide solid, and deaminated in a drying oven at 50-60 ℃ for 3-4 hours for later use;
d. adjusting the pH value of a glyoxal solution with the mass fraction of 40% and the weight percentage of G to 8.0-9.0 at room temperature, heating the glyoxal solution to 40 ℃ in a water bath, adding metered tris (2-aminoethyl) amine-urea polyamide solid according to the amount of urea used for synthesizing the tris (2-aminoethyl) amine-urea polyamide under stirring to ensure that the molar ratio of glyoxal/urea is 0.8-1.2; and continuously heating to 60 ℃, adjusting the pH value to 8.0-9.0 again after the tris (2-aminoethyl) amine-urea polyamide solid is completely dissolved, keeping the temperature for reaction for 1.0-1.5 hours, and adjusting the pH value to 7.0-8.0 after natural cooling to obtain the branched polyamide-glyoxal resin adhesive.
2. Use of the branched polyamide-glyoxal resin adhesive of claim 1 in the industrial production of artificial boards.
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| CN110804415B (en) * | 2019-11-28 | 2021-07-06 | 西南林业大学 | Water-soluble formaldehyde-free wood adhesive and preparation method and application thereof |
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| US3012986A (en) * | 1959-07-09 | 1961-12-12 | Nat Distillers Chem Corp | Urea-formaldehyde modification of branched chain polyamides and product obtained thereby |
| AU6069990A (en) * | 1989-07-12 | 1991-02-06 | Fritz Kramer | Particulate solid aminoplasts and method for their use in sanitary maintenance of biological wastes |
| DE4127614A1 (en) * | 1990-08-30 | 1992-03-05 | Basf Ag | New urea derivs., useful in binders for wood prods. - are obtd. by reaction of specified poly-amine(s) with urea, opt. followed by reaction of the polyurea obtd. with formaldehyde |
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