CN113493679B - Formaldehyde-free feather protein adhesive and preparation method thereof - Google Patents
Formaldehyde-free feather protein adhesive and preparation method thereof Download PDFInfo
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- CN113493679B CN113493679B CN202110854924.8A CN202110854924A CN113493679B CN 113493679 B CN113493679 B CN 113493679B CN 202110854924 A CN202110854924 A CN 202110854924A CN 113493679 B CN113493679 B CN 113493679B
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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
- C09J189/04—Products derived from waste materials, e.g. horn, hoof or hair
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
- C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
Abstract
The invention relates to an aldehyde-free feather protein adhesive which comprises the following components in parts by weight: 35 parts of feather powder, 0.1-0.3 part of bromelain, 72 parts of dispersion medium, 0.5-1 part of activator, 0.3-0.5 part of ethylene glycol diglycidyl ether and 0.9-1.2 parts of curing agent; the dispersion medium is a fructose-guanidine hydrochloride-choline chloride eutectic solvent, the activating agent is a silane coupling agent KH550, and the curing agent is hydroxyethyl melamine. The aldehyde-free feather protein adhesive prepared by the invention degrades feather protein molecules by using bromelain, more effectively improves the types and the number of active groups of feather protein reaction by using an activating agent on the basis of degrading small molecules, recombines the feather protein molecules by using a fructose-guanidine hydrochloride-choline chloride eutectic solvent and ethylene glycol diglycidyl ether to form a protein prepolymer, and finally, adds a curing agent to cure the feather protein adhesive, so that the aldehyde-free feather protein adhesive has the advantages of no release of harmful substances, high reaction activity of products, good solubility and good water retention.
Description
Technical Field
The invention relates to the technical field of biomass adhesives, and particularly relates to an aldehyde-free feather protein adhesive and a preparation method thereof.
Background
Precious wood resources are relatively deficient, artificial forest resources are rich, artificial boards prepared from the fast growing wood of the artificial forest and the adhesive are main raw materials for furniture, floors and interior decoration in human living environments, the total yield of the artificial boards is large, and most of the artificial boards are plywood products. The consumption of the adhesive for the plywood is huge according to the average production of 9 cubic meters of the plywood by each ton of the adhesive, wherein the urea-formaldehyde resin and modified products thereof occupy the leading position of the adhesive. The urea-formaldehyde resin adhesive is widely used in the wood industry due to the advantages of sufficient raw materials, low price, good water solubility and the like, but has the problem of formaldehyde release of products. With the improvement of living standard of people, people pay attention to the problem of environmental pollution. The problem of free formaldehyde emission of the artificial board can be solved by adopting the biomass adhesive to prepare the artificial board, and the method is an important way for solving the problem, but most biomass adhesives have the problem of poor water-resistant bonding performance, and the industrial application of the biomass adhesives is limited. For example, hydrolyzed feather protein can be used as a raw material to prepare an adhesive for an artificial board, so that the problem of free formaldehyde release of the artificial board is solved, but the hydrolyzed feather protein has a large amount of silicified cuticle and large protein molecular weight, so that the problems of poor water solubility, poor water-resistant bonding performance, poor emulsifying property, poor solubility and the like are caused, and the hydrolyzed feather protein is difficult to apply to artificial board production. Therefore, it is needed to provide a new biomass adhesive and a preparation method thereof to solve the problems in the prior art.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to solve the problems and provide the aldehyde-free feather protein adhesive and the preparation method thereof, the adhesive has the advantages of small molecular weight, high activity, good solubility, self-reinforcement, good water-resistant adhesive property and high stability, and the board prepared by the adhesive can meet the water-resistant requirement of an artificial board.
In order to achieve the purpose, the invention adopts the technical scheme that: the aldehyde-free feather protein adhesive comprises the following components in parts by weight: 35 parts of feather powder, 0.1-0.3 part of bromelain, 72 parts of dispersion medium, 0.5-1 part of activator, 0.3-0.5 part of ethylene glycol diglycidyl ether and 0.9-1.2 parts of curing agent.
The formaldehyde-free feather protein adhesive disclosed by the invention is good in water retention, high in solubility, easy to form a cross-linked structure, large in cross-linked density, good in water resistance after curing, stable in performance, stable in quality of prepared plywood products, and obviously reduced in weak interface layer.
Wherein the protein content of the feather powder is 80%, the fineness is 150-180 meshes, and the feather powder is purchased from Tianjin Ronghai International trade company; the bromelain, the dispersion medium, the activator, the ethylene glycol diglycidyl ether and the curing agent are purchased from Beijing chemical Co., ltd.
The bromelain is a protein molecular weight degradation agent, and the bromelain is used as an endoprotease to stretch and degrade feather protein into small molecular polypeptide chain segments, so that the solubility and the stability of the adhesive are improved, the number and the types of reactive groups on hydrolyzed feather protein molecules are increased, the reactivity of the hydrolyzed feather protein molecules is improved, and the viscosity of the adhesive is reduced.
The dispersion medium is a fructose-guanidine hydrochloride-choline chloride eutectic solvent, and can promote the dissolution of feather protein and the Maillard reaction of protein and polysaccharide.
The activating agent is a silane coupling agent KH550, so that the feather cuticle has reactivity, a protein crosslinking system is embedded to form a uniform interpenetrating network structure with chemical bond connection, and the cuticle self-reinforcement in the feather protein is utilized to improve the performance of preparing the adhesive.
The ethylene glycol diglycidyl ether is a protein molecule recombination agent, can recombine hydrolyzed small molecule protein to form a prepolymer with a certain molecular weight, increases the cohesion and uniform stability of adhesive molecules, and simultaneously improves the performance of the adhesive.
The curing agent is hydroxyethyl melamine, and can effectively react with hydroxyl and amino in hydrolyzed feather protein molecules and activated cuticle to form a cross-linked network structure with a rigid structure, so that the adhesive is cured, and the cross-linking density and hardness of the adhesive are improved.
The treatment method of the hydrolyzed feather protein comprises the following steps: adding 35 parts of feather powder into 280 parts of water and 1.4 parts of sodium bisulfite, homogenizing under the homogenizing pressure of 30MPa and the emulsifying pressure of 8MPa for 10 minutes to separate and break the cuticle, adjusting the pH to 9-10, adding an activating agent, stirring at a constant temperature of 60 ℃ for 24 hours, and drying to obtain the activated feather protein powder.
The 72 parts by weight of dispersion medium is prepared by mixing fructose, guanidine hydrochloride and choline chloride according to a weight ratio of 2.
The curing agent is prepared by sequentially adding the following raw materials in parts by weight: 160 parts of 30% glyoxal solution is placed into a reaction kettle, the pH =9.0 is adjusted, the heating is carried out to 60 ℃, 55 parts of melamine is added into the reaction liquid, the temperature is increased to 80 ℃, the heat preservation is carried out for 30 minutes, 100 parts of niobic acid is added, the pH =6.0 is adjusted, the reaction is carried out for 10 minutes, the pH =10.0 is adjusted, the reaction is carried out for 30 minutes, the low-temperature distillation is carried out to obtain the solid content of 50%, and the cooling and discharging are carried out to obtain the curing agent.
The preparation method of the aldehyde-free feather protein adhesive comprises the following steps:
(1) Weighing the components according to the weight part ratio, adding 35 parts of feather meal into 280 parts of water and 1.4 parts of sodium bisulfite, homogenizing under the homogenizing pressure of 30MPa and the emulsifying pressure of 8MPa for 10 minutes to separate and crush the cuticle, adjusting the pH to 9-10, adding an activating agent, stirring at the constant temperature of 60 ℃ for 24 hours, and drying to obtain activated feather protein powder;
(2) Mixing the activated feather protein powder prepared in the step 1 and bromelain, dispersing the mixture in water with the weight 5 times that of the mixture, heating the mixture in a water bath, heating the mixture to 50 ℃, stirring the mixture for 60 minutes, heating the mixture to 80 ℃, preserving the heat for 10 minutes to inactivate the enzyme, and freeze-drying the mixture to prepare a protein raw material;
(3) Mixing the protein raw material prepared in the step 2 with a dispersion medium, uniformly stirring, adjusting the pH =10, adding ethylene glycol diglycidyl ether to react for 2 hours, cooling and discharging to obtain a protein adhesive prepolymer;
(4) And (3) adding a curing agent into the protein adhesive prepolymer prepared in the step (3), and uniformly stirring to obtain the aldehyde-free feather protein adhesive.
The invention has the advantages that:
1) According to the invention, bromelain is used as a protein molecular weight degradation agent, so that feather protein molecules are fully stretched and broken to form small molecules, the number and the types of active groups of a molecular system are increased, the solubility is improved, the uniformity is increased, and the reaction activity is improved;
2) According to the invention, the high-pressure homogenization and the activator are adopted, so that the cuticle on the feather protein can be broken and separated, and effectively combined with the activator, so that the cuticle has reaction activity and is used for enhancing the preparation of the adhesive, and in addition, the adhesive system can be more uniform, and a hard-soft structure is formed when a cross-linking structure is formed, thereby being beneficial to the stability and the gelatinizing property of the adhesive;
3) The invention adopts epoxide glycol diglycidyl ether to connect activated micromolecular feather protein into feather protein glue prepolymer with certain molecular weight, thereby avoiding the problem of low glue joint strength caused by glue penetration caused by hydrolysis of feather protein into micromolecules, and in addition, the formed feather protein glue prepolymer has uniform molecular weight, good permeability, good water solubility and good water-retaining property, the prepared adhesive solves the problems of low glue dry strength, poor glue joint stability, poor water-retaining property and poor water solubility of the common protein glue adhesive, improves the reaction activity, increases the types and the number of functional groups on the feather protein molecules, increases the reaction capacity with a cross-linking agent and reduces the using amount of the curing agent;
4) According to the invention, the rigid cyclic hydroxyethyl melamine formed by catalyzing the niobic acid is used as a curing agent, the synthetic functionality is high, the reactivity with amino is good, a multi-branched cross-linked network structure is easily formed, and meanwhile, the rigid triazine ring is beneficial to increasing the hardness of the adhesive, so that the cohesive force and the adhesive bonding force of the adhesive are improved;
5) The dispersion medium adopted by the invention is a fructose-guanidine hydrochloride-choline chloride eutectic solvent, which can promote the prepolymerization of protein molecules, promote the reaction of epoxy and hydroxyethyl groups with protein, and promote the Maillard reaction of protein and polysaccharide in an adhesive;
6) The aldehyde-free feather protein adhesive prepared by the invention is free of toxic substances, feather protein molecules are degraded by bromelain, the types and the number of active groups for feather protein reaction are effectively improved by using an activating agent on the basis of degrading small molecules, meanwhile, the feather protein molecules are recombined by using a fructose-guanidine hydrochloride-choline chloride eutectic solvent and an epoxide ethylene glycol diglycidyl ether to form a protein adhesive prepolymer, and finally, a curing agent hydroxyethyl melamine is added to cure the feather protein adhesive, so that the aldehyde-free feather protein adhesive is high in efficiency, free of harmful substance release substances, high in product reaction activity, good in solubility and good in water retention.
The present invention will be further described with reference to the following specific examples.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Further, all the component materials used in the examples are known commercially available products.
The percent in the present invention means mass percent unless otherwise specified; but the percentage of the solution, unless otherwise specified, means that the solution 100 ml contains several grams of solute; the percentage between the liquids refers to the ratio of the volumes at 20 ℃.
Example 1
The embodiment provides a no aldehyde feather protein adhesive, the gluing agent prepares material according to following weight ratio:
feather meal 35 kg
Dispersion medium 72 kg
Bromelain 0.1 kg
Activator 0.5 kg
Ethylene glycol diglycidyl ether 0.3 kg
Curing agent 0.9 kg
The embodiment also provides a preparation method of the adhesive, and the specific preparation steps of the adhesive are described in the summary of the invention section above.
Example 2
The embodiment provides a no aldehyde feather protein adhesive, the gluing agent prepares material according to following weight ratio:
feather meal 35 kg
Dispersion medium 72 kg
Bromelain 0.3 kg
Activator 1.0 kg
Ethylene glycol diglycidyl ether 0.5 kg
Curing agent 1.2 kg
The embodiment also provides a preparation method of the adhesive, and the preparation method of the adhesive is the same as that in the embodiment 1.
Comparative example 1
The adhesive related to the comparative example is prepared according to the following weight ratio:
feather meal 35 kg
Dispersion medium 72 kg
Activator 1.0 kg
Ethylene glycol diglycidyl ether 0.5 kg
Curing agent 1.2 kg
Comparative example 1 differs from example 2 only in that: the material of comparative example 1 was free of bromelain.
Comparative example 2
The adhesive related to the comparative example is prepared according to the following weight ratio:
feather meal 35 kg
Water 72 kg
Bromelain 0.3 kg
Activator 1.0 kg
Ethylene glycol diglycidyl ether 0.5 kg
Curing agent 1.2 kg
Comparative example 2 differs from example 2 only in that: comparative example 2 the dispersion medium in example 2 was replaced with water.
Comparative example 3
The adhesive related to the comparative example is prepared according to the following weight ratio:
feather meal 35 kg
Dispersion medium 72 kg
Bromelain 0.3 kg
Ethylene glycol diglycidyl ether 0.5 kg
Curing agent 1.2 kg
Comparative example 3 differs from example 2 only in that: the starting material of comparative example 3 contained no activator.
Comparative example 4
The adhesive related to the comparative example is prepared according to the following weight ratio:
feather meal 35 kg
Dispersion medium 72 kg
Bromelain 0.3 kg
Activator 1.0 kg
Ethylene glycol diglycidyl ether 0.5 kg
Comparative example 4 differs from example 2 only in that: the raw materials of comparative example 4 contained no curing agent.
Comparative example 5
The adhesive of this comparative example was obtained from kyotong thousand-son wood group ltd using the same weight of melamine-modified urea resin (E0 grade) as the adhesive of example 2 and having a molar ratio of 1.01.
Test examples
Three-layer plywood was prepared by using the adhesives of examples 1-2 and comparative examples 1-5 of the present invention, respectively.
Basswood veneer: drying the water content to 10%; the dimensions 40cm by 0.15cm.
The preparation method comprises the following normal preparation processes:
sizing: applying glue on two sides of the core plate, wherein the glue application amount is 400g/m 2 。
The pressure, temperature and time are respectively as follows: 0.8MPa, 110 ℃ and 6 minutes.
The performance of the transverse spliced product is detected according to a detection method of GB/T17657-2013 physicochemical property experimental method for artificial boards and decorative artificial boards, and the detection result is shown in Table 1.
TABLE 1 plywood bond Strength
Experimental results show that the wet waterproof bonding strength of the plywood prepared by the aldehyde-free feather protein adhesive can reach 1.52MPa according to the detection of type II plywood requirements, the dry strength can reach 2.33MPa, the glue failure time in water boiling can reach 36 hours, and the improvement is remarkable compared with a control example.
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 (5)
1. The formaldehyde-free feather protein adhesive is characterized by comprising the following components in parts by weight: 35 parts of feather powder, 0.1-0.3 part of bromelain, 72 parts of dispersion medium, 0.5-1 part of activator, 0.3-0.5 part of ethylene glycol diglycidyl ether and 0.9-1.2 parts of curing agent;
the dispersion medium is a fructose-guanidine hydrochloride-choline chloride eutectic solvent, the activator is a silane coupling agent KH550, the ethylene glycol diglycidyl ether is a protein molecule recombination agent, and the curing agent is hydroxyethyl melamine;
the curing agent is prepared by sequentially adding the following raw materials in parts by weight: putting 160 parts of 30% glyoxal solution into a reaction kettle, adjusting the pH value to 9.0, heating to 60 ℃, adding 55 parts of melamine into the reaction liquid, heating to 80 ℃, keeping the temperature for 30 minutes, adding 100 parts of niobic acid, adjusting the pH value to 6.0, reacting for 10 minutes, adjusting the pH value to 10.0, reacting for 30 minutes, distilling at low temperature to obtain 50% solid content, cooling and discharging to obtain the curing agent;
the preparation method of the aldehyde-free feather protein adhesive comprises the following steps:
(1) Weighing the components according to the weight part ratio, adding 35 parts of feather powder into 280 parts of water and 1.4 parts of sodium bisulfite, homogenizing under the homogenizing pressure of 30MPa and the emulsifying pressure of 8MPa for 10 minutes to separate and crush cuticle, adjusting the pH to 9-10, adding an activating agent, stirring at the constant temperature of 60 ℃ for 24 hours, and drying to obtain activated feather protein powder;
(2) Mixing the activated feather protein powder prepared in the step 1 and bromelain, dispersing the mixture in water with the weight 5 times that of the mixture, heating the mixture to 50 ℃ in water bath, stirring the mixture for 60 minutes, heating the mixture to 80 ℃, preserving the heat for 10 minutes to inactivate the enzyme, and freeze-drying the mixture to prepare a protein raw material;
(3) Mixing the protein raw material prepared in the step 2 with a dispersion medium, uniformly stirring, adjusting the pH =10, adding ethylene glycol diglycidyl ether to react for 2 hours, cooling and discharging to obtain a protein adhesive prepolymer;
(4) And (3) adding a curing agent into the protein adhesive prepolymer prepared in the step (3), and uniformly stirring to obtain the aldehyde-free feather protein adhesive.
2. The aldehyde-free feather protein adhesive of claim 1, wherein: the feather powder contains 80% of protein and has fineness of 150-180 meshes.
3. The aldehyde-free feather protein adhesive of claim 1, wherein: the feather powder is purchased from Tianjin Ronghai International trade company, and the bromelain, the dispersion medium, the activator, the ethylene glycol diglycidyl ether and the curing agent are purchased from Beijing chemical industry company, inc.
4. The aldehyde-free feather protein adhesive of claim 1, wherein: the 72 parts by weight of dispersion medium is prepared by mixing fructose, guanidine hydrochloride and choline chloride according to the weight ratio of 2.
5. A method for preparing the aldehyde-free feather protein adhesive of any one of claims 1 to 4, comprising the following steps:
(1) Weighing the components according to the weight part ratio, adding 35 parts of feather powder into 280 parts of water and 1.4 parts of sodium bisulfite, homogenizing under the homogenizing pressure of 30MPa and the emulsifying pressure of 8MPa for 10 minutes to separate and crush cuticle, adjusting the pH to 9-10, adding an activating agent, stirring at the constant temperature of 60 ℃ for 24 hours, and drying to obtain activated feather protein powder;
(2) Mixing the activated feather protein powder prepared in the step 1 and bromelain, dispersing the mixture in water with the weight 5 times that of the mixture, heating the mixture to 50 ℃ in water bath, stirring the mixture for 60 minutes, heating the mixture to 80 ℃, preserving the heat for 10 minutes to inactivate the enzyme, and freeze-drying the mixture to prepare a protein raw material;
(3) Mixing the protein raw material prepared in the step 2 with a dispersion medium, uniformly stirring, adjusting the pH =10, adding ethylene glycol diglycidyl ether to react for 2 hours, cooling and discharging to obtain a protein adhesive prepolymer;
(4) And (3) adding a curing agent into the protein adhesive prepolymer prepared in the step (3), and uniformly stirring to obtain the aldehyde-free feather protein adhesive.
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| CN202110854924.8A CN113493679B (en) | 2021-07-28 | 2021-07-28 | Formaldehyde-free feather protein adhesive and preparation method thereof |
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| CN202110854924.8A CN113493679B (en) | 2021-07-28 | 2021-07-28 | Formaldehyde-free feather protein adhesive and preparation method thereof |
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|---|---|---|---|---|
| GB1423558A (en) * | 1972-08-05 | 1976-02-04 | Kuraray Co Ltd Asahi Co Ltd | Adhesive composition |
| US7066995B1 (en) * | 2004-03-19 | 2006-06-27 | The United States Of America As Represented By The Secretary Of Agriculture | Compositions and films comprised of avian feather keratin |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN105969304A (en) * | 2016-05-31 | 2016-09-28 | 北京林业大学 | Soybean aldehyde-free adhesive and preparation method thereof |
| CN109504342A (en) * | 2018-11-23 | 2019-03-22 | 南京林业大学 | A kind of no aldehyde albumen adhesive and preparation method thereof |
| CN111876130A (en) * | 2020-07-27 | 2020-11-03 | 南京林业大学 | Bio-based protein adhesive for artificial board and preparation method thereof |
| CN112679752A (en) * | 2020-12-25 | 2021-04-20 | 大连工业大学 | Preparation method of glycosylated protein based on eutectic solvent |
-
2021
- 2021-07-28 CN CN202110854924.8A patent/CN113493679B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1423558A (en) * | 1972-08-05 | 1976-02-04 | Kuraray Co Ltd Asahi Co Ltd | Adhesive composition |
| US7066995B1 (en) * | 2004-03-19 | 2006-06-27 | The United States Of America As Represented By The Secretary Of Agriculture | Compositions and films comprised of avian feather keratin |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN105969304A (en) * | 2016-05-31 | 2016-09-28 | 北京林业大学 | Soybean aldehyde-free adhesive and preparation method thereof |
| CN109504342A (en) * | 2018-11-23 | 2019-03-22 | 南京林业大学 | A kind of no aldehyde albumen adhesive and preparation method thereof |
| CN111876130A (en) * | 2020-07-27 | 2020-11-03 | 南京林业大学 | Bio-based protein adhesive for artificial board and preparation method thereof |
| CN112679752A (en) * | 2020-12-25 | 2021-04-20 | 大连工业大学 | Preparation method of glycosylated protein based on eutectic solvent |
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