CN111171314B - Modified PAE resin crosslinking agent, modified adhesive and application - Google Patents
Modified PAE resin crosslinking agent, modified adhesive and application Download PDFInfo
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- CN111171314B CN111171314B CN202010067335.0A CN202010067335A CN111171314B CN 111171314 B CN111171314 B CN 111171314B CN 202010067335 A CN202010067335 A CN 202010067335A CN 111171314 B CN111171314 B CN 111171314B
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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
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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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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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
- C09J11/08—Macromolecular additives
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
Abstract
The invention relates to a modified PAE resin crosslinking agent, a modified adhesive and application. The modified PAE resin crosslinking agent is prepared from water, adipic acid, diethylenetriamine, a modifier and epichlorohydrin. The embodiment of the invention provides a modified PAE resin cross-linking agent, wherein the main chain of the cross-linking agent is grafted with catechol groups with an adhesion function. The invention unexpectedly discovers that the initial viscosity of the prepared protein adhesive is obviously improved, the prepressing molding time is greatly shortened, the water-resistant bonding strength is improved and the national standard requirements are met by grafting the catechol functional group on the main chain of the PAE and adopting a high-activity crosslinking technology.
Description
Technical Field
The invention relates to an adhesive, in particular to a modified PAE resin cross-linking agent, a modified adhesive and application.
Background
The adhesives used in the current artificial board industry still mainly comprise formaldehyde synthetic resins, and harmful gases such as free formaldehyde and phenol volatilized in production, transportation and use cause great harm to human health, so that the research and development strength of the environment-friendly wood adhesives is continuously enhanced, and the novel biomass-based formaldehyde-free wood adhesive is expected to thoroughly solve the problem of formaldehyde pollution.
In a plurality of biomass raw materials such as lignin, tannin, protein, starch, chitosan and the like, the soybean protein becomes one of ideal raw materials for preparing the wood adhesive by virtue of the advantages of rich resources, renewability, low price and the like. The prepared soybean protein adhesive has the advantages of short production period, strong reproducibility, low price, high reaction activity and the like, is easy to operate, and can be used for hot pressing and cold pressing. However, the soybean protein contains a large amount of-OH and-NH2Hydrophilic groups such as-COOH and-CONH, the soybean protein adhesive has high water absorption, the hydrogen bonding effect is easily destroyed under the conditions of humidity, water bubble or boiling, the intermolecular force is obviously weakened due to the isolation of water molecules, the water resistance of the soybean protein adhesive is poor, the bonding strength is low, and the strong bonding of the adhesive is influencedDegree and range of use. To address these shortcomings, various methods have been developed to modify them. The polyamide polyamine epichlorohydrin (PAE) is a commonly used crosslinking agent in the soybean protein adhesive modification method, contains a large number of cationic active groups (azadine heterocycles), and can perform crosslinking reaction with active groups such as amino groups, carboxyl groups, hydroxyl groups and the like on a soybean protein molecular chain and on the surface of wood to generate a stable three-dimensional space network structure, so that the bonding strength and the water resistance of the soybean protein adhesive are improved.
However, in practical production, the artificial board prepared from the PAE modified soy protein adhesive has the problems of poor initial adhesion, poor prepressing performance and the like, so that the prepressing time is prolonged (3-4 hours), the board is difficult to be mounted, and the core cannot be repaired. The reason is that the raw material base material for manufacturing the artificial board in industry has too high and unstable water content, a monomolecular hydration layer is easily formed between the surfaces of the base materials, the hydration film seriously prevents the close chemical contact between the adhesive and the base material, the surface energy of an adherend providing a driving force for adhesion is greatly reduced, the wet adhesion strength is reduced or even eliminated, the prepressing time of the artificial board is prolonged, and the prepressing performance is seriously reduced.
Disclosure of Invention
The embodiment of the invention provides a modified PAE resin crosslinking agent, wherein a main chain of the crosslinking agent is grafted with catechol groups with an adhesion function. The invention unexpectedly discovers that the initial viscosity of the prepared protein adhesive is obviously improved, the prepressing molding time is greatly shortened, the water-resistant bonding strength is improved and the national standard requirements are met by grafting the catechol functional group on the main chain of the PAE and adopting a high-activity crosslinking technology.
A modified PAE resin cross-linking agent is prepared from the following raw materials in parts by weight:
wherein the modifier is selected from one or more of hydrogenated caffeic acid, 3, 4-dihydroxy benzaldehyde, 2-chloro-3, 4-dihydroxy acetophenone, tannic acid and gallic acid.
The water is preferably deionized water.
In some embodiments of the present invention, the modified PAE resin crosslinker is made from raw materials comprising, by weight:
in some embodiments of the present invention, the raw material of the modified PAE resin crosslinker further comprises a pH adjuster, such as hydrochloric acid, sodium hydroxide, and the like.
The invention also provides a preparation method of the modified PAE resin crosslinking agent, which comprises the following steps:
1) preparing a polyamide polyamine intermediate from adipic acid and diethylenetriamine;
2) reacting the polyamide polyamine intermediate with a modifier to prepare a grafted catechol group prepolymer;
3) and reacting the grafted catechol group prepolymer with epoxy chloropropane to prepare the modified PAE resin crosslinking agent.
In the preparation method, the step 1) can be specifically mixing adipic acid and diethylenetriamine according to the proportion, heating, evaporating water, cooling to 120 ℃ or below, adding water, and stirring to a homogeneous phase to obtain the polyamide polyamine intermediate. Further, this step may be performed in a reaction vessel. Wherein the temperature rise is preferably 160-180 ℃; the amount of water (preferably deionized water) added is preferably adjusted to a solids content of 30 to 35% by weight. This step can be carried out under nitrogen protection.
In the preparation method, the step 2) can be specifically mixing the polyamide polyamine intermediate and the modifier according to the proportion, and fully reacting to prepare the grafted catechol group prepolymer. Further, the reaction temperature in the step is preferably 25-30 ℃.
In the preparation method, the step 3) can be specifically that epichlorohydrin is added into the grafted catechol group prepolymer and the reaction is carried out at 65-70 ℃; and after the reaction is finished, adjusting the pH value to 3-4 to obtain the modified PAE resin crosslinking agent. Further, the reaction temperature in this step is more preferably 65 ℃. The heating is generally stopped immediately when the viscosity of the solution reaches the requirement.
The invention also comprises the modified PAE resin crosslinking agent prepared by the method.
The principle of the preparation method of the modified PAE resin cross-linking agent disclosed by the embodiment of the invention is that a polyamide polyamine main chain containing high-activity amino groups can perform graft copolymerization with multiple groups (carboxyl, aldehyde and the like), so that a substance with catechol groups is grafted to the main chain of the PAE, and is adhered to a target surface by different mechanisms such as hydrogen bonds, metal oxide coordination or cation-pi interaction, and good underwater adhesion performance is endowed.
The invention also provides application of the modified PAE resin cross-linking agent in preparation of a protein adhesive. Experiments show that the protein adhesive prepared by the modified PAE resin crosslinking agent has higher bonding strength, good water resistance and no formaldehyde release, and can realize single-board bonding with high water content.
The invention also provides a modified protein adhesive which is prepared from the following raw materials in parts by weight:
in some embodiments of the present invention, the modified protein adhesive is prepared from the following raw materials in parts by weight:
in some embodiments of the invention, the protein meal is vegetable protein meal.
In some embodiments of the present invention, the protein meal is one or more of soybean meal, maple meal, peanut meal, castor meal, cottonseed meal, rapeseed meal, and distillers' grains.
In some embodiments of the invention, the protein meal has a particle size of 70-500 mesh.
In some embodiments of the invention, the protein meal has a particle size of 100-400 mesh.
In some embodiments of the invention, the protein meal has a particle size of 200-250 mesh.
The protein meal in the particle size range is powdery, and the powder is easy to disperse and is beneficial to fully contacting and reacting with the cross-linking agent.
In some embodiments of the invention, the protein meal is defatted protein meal.
In some embodiments of the invention, the protein content of the protein meal is above 40% (w/w).
In some embodiments of the invention, the protein content of the protein meal is 40-60% (w/w).
In some embodiments of the invention, the protein content of the protein meal is 50% (w/w).
In some embodiments of the present invention, the alkali is one or a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and barium hydroxide.
In some embodiments of the invention, the modified protein adhesive has a solids content of 25 to 45 wt%.
In some embodiments of the invention, the viscosity of the modified protein adhesive is 400-2000MPa "s.
In some embodiments of the invention, the modified protein adhesive has an active period of 20 to 30 days.
The invention also provides a preparation method of the modified protein adhesive, which comprises the following steps:
a) mixing protein meal with a mixed solution of alkali and urea, and reacting to obtain protein meal degradation liquid;
b) and mixing the protein meal degradation liquid with the modified PAE resin cross-linking agent, and reacting to obtain the protein adhesive.
In the preparation method, the mixed solution of alkali and urea can be added into the protein meal under the condition of stirring in the step a), the temperature is raised, and the stirring reflux reaction is carried out, so as to obtain the protein meal degradation liquid. Further, the temperature of the stirring reflux reaction is preferably 45 to 100 ℃ and the time is preferably 1 to 3 hours.
In the preparation method, the modified PAE resin crosslinking agent in the step b) can be added into the soybean meal under the stirring condition for reaction. The reaction temperature is preferably 40 to 65 ℃ and the reaction time is preferably 1 to 3 hours.
In some embodiments, mechanical agitation may be used during mixing in steps a) and b), at a speed of 600-.
In some embodiments of the present invention, the alkali and the urea can be dispersed in water and mixed to obtain a mixed solution of the alkali and the urea. Further, the blending can be performed by mechanical stirring, for example, at 800-.
The invention also discloses the modified protein adhesive prepared by the method.
The invention also comprises the application of the modified protein adhesive in the fields of wood, bamboo, furniture, printed matters, decoration, buildings and the like.
In particular, the invention also comprises wood products, bamboo products, printed matters, ornaments, buildings and the like containing the modified protein adhesive, such as artificial boards such as plywood, flakeboard, medium density fiberboard and laminated wood board.
The modified protein adhesive disclosed by the embodiment of the invention has no formaldehyde release, so that the manufactured artificial board has no formaldehyde release; the adhesive has good prepressing performance, high adhesive bonding strength and excellent water resistance, can meet the requirements of II types of plywood, does not crack after being boiled in water at 100 ℃, and can be used for producing artificial boards such as plywood, shaving board, medium density fiberboard, laminated wood board and the like.
The main raw material bean pulp of the embodiment of the invention is grain crop processing residues, is a renewable resource, can simultaneously solve the problems of recycling of grain crop wastes and high cost of the biomass adhesive, solves the problem of excessive dependence of the synthetic adhesive on fossil resources, meets the requirements of environmental protection and sustainable development, and has important economic and social benefits.
The preparation method of the modified protein adhesive is simple and feasible in process and is suitable for industrial production.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The soybean meal used below is defatted soybean meal, the protein content is 50% (w/w), and the particle size is 150-200 mesh.
Example 1
1. The embodiment provides a modified PAE resin crosslinking agent, which is prepared from the following raw materials in parts by weight:
this embodiment also provides a method for preparing the modified PAE resin crosslinking agent, comprising:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) Preparing a prepolymer of the grafted catechol group. And adding the polyamide polyamine intermediate and 15kg of 3, 4-dihydroxy benzaldehyde into a reaction kettle, and stirring and reacting at 25-30 ℃ to obtain the grafted catechol group prepolymer.
(3) And (3) preparing a modified PAE resin crosslinking agent. And adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the modified PAE resin crosslinking agent.
2. The embodiment also provides a modified protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified protein adhesive, which comprises the following steps:
(1) dispersing 5kg of potassium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) adding the obtained soybean meal degradation liquid and 15kg of modified PAE resin cross-linking agent into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The modified protein adhesive of this embodiment is used to manufacture three-layer plywood with the following manufacturing process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100 s/min);
the plywood bonding strength (class II) of the three-ply plywood prepared in the example was tested according to GB/T9846-.
Example 2
1. The embodiment provides a modified PAE resin crosslinking agent, which is prepared from the following raw materials in parts by weight:
this embodiment also provides a method for preparing the modified PAE resin crosslinking agent, comprising:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) Preparing a prepolymer of the grafted catechol group. Adding the polyamide polyamine intermediate and 15kg of hydrogenated caffeic acid into a reaction kettle, and stirring and reacting for a certain time at the temperature of 25-30 ℃ to obtain the target product grafted catechol group prepolymer.
(3) And (3) preparing the modified PAE resin crosslinking agent. And adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the modified PAE resin.
2. The embodiment also provides a modified protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified protein adhesive, which comprises the following steps:
(1) dispersing 5kg of sodium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) adding the obtained soybean meal degradation liquid and 15kg of modified PAE resin cross-linking agent into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The modified protein adhesive of this embodiment is used to manufacture three-layer plywood with the following manufacturing process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The bonding strength (class II) of the three-ply plywood prepared in this example was tested according to GB/T9846-.
Example 3
1. The embodiment provides a modified PAE resin crosslinking agent, which is prepared from the following raw materials in parts by weight:
this embodiment also provides a method for preparing the modified PAE resin crosslinking agent, comprising:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) Preparing a prepolymer of the grafted catechol group. Adding the polyamide polyamine intermediate and 15kg of 2-chloro-3, 4-dihydroxy acetophenone into a reaction kettle, and stirring and reacting for a certain time at the temperature of 25-30 ℃ to obtain the target product grafted catechol group prepolymer.
(3) And (3) preparing the modified PAE resin crosslinking agent. And adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the modified PAE resin.
2. The embodiment also provides a modified protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified protein adhesive, which comprises the following steps:
(1) dispersing 5kg of calcium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) adding the obtained soybean meal degradation liquid and 15kg of modified PAE resin cross-linking agent into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The modified protein adhesive of the embodiment is adopted to manufacture a three-layer plywood by the following preparation process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The bonding strength (class II) of the three-ply plywood prepared in this example was tested according to GB/T9846-.
Example 4
1. The embodiment provides a modified PAE resin crosslinking agent, which is prepared from the following raw materials in parts by weight:
this embodiment also provides a method for preparing the modified PAE resin crosslinking agent, comprising:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) Preparing a prepolymer of the grafted catechol group. And adding the polyamide polyamine intermediate and 15kg of tannic acid into a reaction kettle, and stirring and reacting for a certain time at the temperature of 25-30 ℃ to obtain the target product grafted catechol group prepolymer.
(3) And (3) preparing a modified PAE resin crosslinking agent. And adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the modified PAE resin crosslinking agent.
2. The embodiment also provides a modified protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified protein adhesive, which comprises the following steps:
(1) dispersing 5kg of barium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) adding the obtained soybean meal degradation liquid and 15kg of modified PAE resin cross-linking agent into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The modified protein adhesive of the embodiment is adopted to manufacture the three-layer plywood by the following preparation process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-325g/m2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The bonding strength (class II) of the three-ply plywood prepared in this example was tested according to GB/T9846-.
Example 5
1. The embodiment provides a modified PAE resin crosslinking agent, which is prepared from the following raw materials in parts by weight:
this embodiment also provides a method for preparing the modified PAE resin crosslinking agent, comprising:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) Preparing a prepolymer of the grafted catechol group. Adding the polyamide polyamine and 15kg of gallic acid into a reaction kettle, and stirring and reacting for a certain time at the temperature of 25-30 ℃ to obtain the target product grafted catechol group prepolymer.
(3) And (3) preparing a modified PAE resin crosslinking agent. And adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the modified PAE resin crosslinking agent.
2. The embodiment also provides a modified protein adhesive, which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified protein adhesive, which comprises the following steps:
(1) dispersing 5kg of lithium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) adding the obtained soybean meal degradation liquid and 15kg of modified PAE resin cross-linking agent into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The modified protein adhesive of the embodiment is adopted to manufacture the three-layer plywood by the following preparation process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The bonding strength (class II) of the three-ply plywood prepared in this example was tested according to GB/T9846-.
Comparative example 1
1. The PAE cross-linking agent of the comparative example is prepared from the following raw materials in parts by weight:
the comparative example PAE crosslinker preparation method included:
(1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. After the water is evaporated to dryness, immediately stopping heating, when the temperature is reduced to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) And (3) preparing a PAE crosslinking agent. Adding water into the polyamide polyamine intermediate, slowly dropwise adding 10kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the PAE crosslinking agent.
2. The comparative example also provides a protein adhesive, which is prepared from the following raw materials in parts by weight:
the comparative example also provides a preparation method of the protein adhesive, which comprises the following steps:
(1) dispersing 5kg of potassium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) and adding the obtained soybean meal degradation liquid and 15kg of the PAE resin cross-linking agent in the comparative example into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The three-layer plywood is manufactured by adopting the protein adhesive in the comparative example according to the following preparation process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100 s/min);
the bonding strength (class II) of the three-ply plywood prepared in the comparative example was tested according to GB/T9846-.
Comparative example 2
1. The comparative example provides a PAE crosslinking agent, which is prepared from the following raw materials in parts by weight:
the comparative example PAE crosslinker preparation method included: (1) preparation of polyamide polyamine intermediate. 15kg of adipic acid and 10kg of diethylenetriamine are added into a reaction kettle, and stirred for 30min after the raw materials are completely mixed and melted. Raising the temperature to the preset reaction temperature, starting to evaporate the water in the solution, and keeping the temperature for 5 hours. And (3) drying the water by distillation, immediately stopping heating, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 30 wt%, stirring to a homogeneous phase, and stopping stirring. The whole process is protected by introducing nitrogen.
(2) And preparing a PAE cross-linking agent. Adding water into the polyamide polyamine intermediate, slowly dropwise adding 15kg of epoxy chloropropane, heating to 65 ℃ after dropwise adding, keeping the temperature, stopping heating immediately when the viscosity of the solution meets the requirement, dropwise adding HCl with the mass fraction of 10% to adjust the pH value to 3-4, and thus obtaining the PAE crosslinking agent.
2. The comparative example also provides a protein adhesive which is prepared from the following raw materials in parts by weight:
the comparative example also provides a preparation method of the protein adhesive, which comprises the following steps:
(1) dispersing 5kg of sodium hydroxide and 10kg of urea in 100kg of water at normal temperature, adding 30kg of soybean meal under the stirring condition of the rotating speed of 1000 revolutions per minute, heating to 65 ℃, and stirring and refluxing for 3 hours to obtain soybean meal degradation liquid;
(2) and adding the obtained soybean meal degradation liquid and 15kg of the PAE resin cross-linking agent in the comparative example into a reaction kettle, carrying out stirring reflux reaction for 2 hours at the temperature of 60 ℃, and cooling to normal temperature to obtain the protein adhesive.
3. The three-layer plywood is manufactured by adopting the protein adhesive in the comparative example according to the following preparation process parameters:
veneer: poplar, the water content is 15-30%, and the thickness is 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60 min; (ii) a
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100s/min)
The bonding strength (class II) of the three-ply plywood prepared in the comparative example was tested according to GB/T9846-.
TABLE 1 Performance index of protein Adhesives
| Prepressing time (min) | Bonding Strength (MPa) | Solid content (w)t％) | |
| Example 1 | 45 | 1.13±0.21 | 34.5 |
| Example 2 | 42 | 1.23±0.18 | 36.2 |
| Example 3 | 41 | 1.30±0.15 | 38.9 |
| Example 4 | 39 | 1.35±0.13 | 40.1 |
| Example 5 | 37 | 1.40±0.19 | 41.0 |
| Comparative example 1 | ≥180 | 1.02±0.15 | 33.9 |
| Comparative example 2 | ≥180 | 1.09±0.20 | 35.6 |
The detection results in table 1 show that the initial viscosity of the modified protein adhesive prepared by using the PAE crosslinked resin provided by the invention is remarkably improved, the pre-pressing forming time is greatly shortened, and the water-resistant bonding strength is improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (15)
1. A modified PAE resin cross-linking agent is prepared from the following raw materials in parts by weight:
wherein the modifier is selected from one or more of hydrogenated caffeic acid, 3, 4-dihydroxy benzaldehyde, 2-chloro-3, 4-dihydroxy acetophenone, tannic acid and gallic acid.
2. The modified PAE resin crosslinking agent of claim 1, which is prepared from the following raw materials in parts by weight:
3. a process for the preparation of a modified PAE resin crosslinker as claimed in claim 1 or 2 comprising the steps of:
1) preparing a polyamide polyamine intermediate by using adipic acid and diethylenetriamine as raw materials;
2) reacting the polyamide polyamine intermediate with a modifier to prepare a grafted catechol group prepolymer;
3) and reacting the grafted catechol group prepolymer with epoxy chloropropane to prepare the modified PAE resin crosslinking agent.
4. The preparation method according to claim 3, wherein the step 1) comprises mixing adipic acid and diethylenetriamine according to a ratio, heating, evaporating to remove water, cooling to 120 ℃ or below, adding water, and stirring to a homogeneous phase to obtain a polyamide polyamine intermediate; and/or the presence of a gas in the gas,
step 2) mixing the polyamide polyamine intermediate with a modifier according to a ratio, and fully reacting to obtain a grafted catechol group prepolymer; and/or the presence of a gas in the gas,
step 3) comprises adding epichlorohydrin into the grafted catechol group prepolymer, and reacting at 65-70 ℃; and after the reaction is finished, adjusting the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
5. The preparation method according to claim 4, wherein the temperature of the temperature rise in step 1) is 160-180 ℃; the amount of water added is adjusted to a solid content of 30-35 wt%; and/or the presence of a gas in the gas,
step 2), the reaction temperature is 25-30 ℃; and/or the presence of a gas in the gas,
step 3) the reaction temperature was 65 ℃.
6. A modified PAE resin crosslinker prepared by the process of any of claims 3 to 5.
7. Use of the modified PAE resin crosslinker of any of claims 1, 2, 6 in the preparation of a protein adhesive.
8. The modified protein adhesive is prepared from the following raw materials in parts by weight:
9. the modified protein adhesive of claim 8, which is prepared from the following raw materials in parts by weight:
10. the modified protein adhesive of claim 8 or 9, wherein,
the protein meal is plant protein meal; and/or the presence of a gas in the gas,
the granularity of the protein meal is 70-500 meshes; and/or the presence of a gas in the gas,
the protein content in the protein meal is more than 40 wt%.
11. The modified protein adhesive of claim 8 or 9, wherein,
the protein meal is one or more of bean pulp, maple pulp, peanut meal, castor meal, cottonseed meal, rapeseed meal and alcohol lees; and/or the presence of a gas in the gas,
the granularity of the protein meal is 100-400 meshes; and/or the presence of a gas in the gas,
the protein content in the protein meal is 40-60 wt%.
12. The modified protein adhesive as claimed in claim 8 or 9, wherein the protein meal has a particle size of 200-250 meshes.
13. The modified protein adhesive of claim 8 or 9, wherein the protein meal is defatted protein meal.
14. The method for preparing the modified protein adhesive according to any one of claims 8 to 13, comprising the following steps:
a) mixing protein meal with a mixed solution of alkali and urea, and reacting to obtain protein meal degradation liquid;
b) and mixing the protein meal degradation liquid with the modified PAE resin cross-linking agent, and reacting to obtain the protein adhesive.
15. A wood work, bamboo work, print, ornament or building containing the modified protein adhesive of any one of claims 8 to 13.
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| CN111607337B (en) * | 2020-05-22 | 2021-06-04 | 湖北恒昊包装科技有限公司 | Adhesive for corrugated board explosion-proof line and preparation method thereof |
| CN112265098B (en) * | 2020-10-20 | 2022-05-06 | 德华兔宝宝装饰新材股份有限公司 | Preparation method of chemical color-changing composite floor |
| CN114736651B (en) * | 2022-04-15 | 2024-01-05 | 书香门地集团股份有限公司 | Tough soybean protein adhesive and preparation method and application thereof |
| CN114575188B (en) * | 2022-05-05 | 2022-07-29 | 山东奥赛新材料有限公司 | Synthetic method of high-solid-content PAE resin |
| CN116622060B (en) * | 2022-08-15 | 2024-03-12 | 徐州安联木业有限公司 | Multifunctional biomass crosslinking agent, vegetable protein adhesive and preparation method thereof |
| CN116606434A (en) * | 2023-05-31 | 2023-08-18 | 陕西科技大学 | Dendritic polymer complexing Al composite chrome-free tanning agent and preparation method and application thereof |
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