CN113913152A - Spirulina protein adhesive and preparation method and application thereof - Google Patents
Spirulina protein adhesive and preparation method and application thereof Download PDFInfo
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- CN113913152A CN113913152A CN202111171928.2A CN202111171928A CN113913152A CN 113913152 A CN113913152 A CN 113913152A CN 202111171928 A CN202111171928 A CN 202111171928A CN 113913152 A CN113913152 A CN 113913152A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 101
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 101
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 97
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 97
- 240000002900 Arthrospira platensis Species 0.000 title claims abstract description 82
- 235000016425 Arthrospira platensis Nutrition 0.000 title claims abstract description 82
- 229940082787 spirulina Drugs 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011120 plywood Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000004026 adhesive bonding Methods 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 235000018102 proteins Nutrition 0.000 description 74
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 17
- 108090000765 processed proteins & peptides Proteins 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 6
- 108010073771 Soybean Proteins Proteins 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- -1 amino, carboxyl Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940001941 soy protein Drugs 0.000 description 2
- 235000019710 soybean protein Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RMZLKDQEPIENPJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound OCC(C)(C)CO.C1OC1COCC1CO1 RMZLKDQEPIENPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 108010075254 C-Peptide Proteins 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000007065 protein hydrolysis Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 108010027322 single cell proteins Proteins 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27G—ACCESSORY MACHINES OR APPARATUS FOR WORKING WOOD OR SIMILAR MATERIALS; TOOLS FOR WORKING WOOD OR SIMILAR MATERIALS; SAFETY DEVICES FOR WOOD WORKING MACHINES OR TOOLS
- B27G11/00—Applying adhesives or glue to surfaces of wood to be joined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the field of aldehyde-free environment-friendly adhesives, and discloses a spirulina protein adhesive as well as a preparation method and application thereof. The spirulina protein adhesive is prepared from the following raw materials in parts by weight: 4-10 parts of spirulina protein powder, 40-70 parts of water, 0.1-0.6 part of modifier and 1-8 parts of cross-linking agent. The adhesive prepared by the method has good adhesive bonding performance, simple preparation process, lower cost and low energy consumption. The invention does not contain harmful volatile matters such as formaldehyde, phenol and the like, gets rid of the dependence on petrochemical resources from the material source, and the material source has the renewable capability. The common plywood prepared by the adhesive disclosed by the invention has higher bonding strength and good water resistance.
Description
Technical Field
The invention belongs to the field of aldehyde-free environment-friendly adhesives, and particularly relates to a spirulina protein adhesive as well as a preparation method and application thereof.
Background
According to the grain and agriculture organization data of the United nations, the yield of the global artificial board in 2017 is about 4.2 hundred million m3. With the steady development of the wood industry, the annual output of the artificial boards can be continuously and stably increased. The wood industry needs to consume a large amount of adhesive every year, and the use of the adhesive accounts for about 75% of the global adhesive yield. According to conservative estimation, the adhesive used in the wood industry in China far exceeds 1500 ten thousand tons. However, the adhesives used in the production of the current artificial boards are still dominated by aldehyde adhesives, mainly including urea formaldehyde, phenol formaldehyde and melamine formaldehyde adhesives. The aldehyde adhesive is widely applied due to higher bonding performance and water resistance, excellent durability and proper viscosity, but the adhesive and products thereof can release harmful volatile matters such as formaldehyde or phenol and the like in the production and use processes, and are easily absorbed by human bodies so as to harm the human health. The international agency for research on cancer (IARC) defines formaldehyde as a class I carcinogen, which can lead to the development of a variety of diseases. On the other hand, although petroleum fossil-based non-renewable resources are abundant on earth, their reserves have been becoming smaller and smaller due to the enormous demand of various industries over the years since the last century, and at the same time, the deterioration of environmental conditions has been aggravated due to the excessive use of petroleum fossil fuels. Therefore, the search for environmentally friendly, aldehyde-free, renewable adhesives in the wood industry is an important and pressing task.
In recent years, wood adhesives prepared by utilizing natural materials such as tannin, lignin, starch, protein and the like are developed continuously, and the wood adhesives are expected to become environment-friendly adhesives for replacing formaldehyde in the future. The synthesis of adhesives by using proteins as raw materials has become a research hotspot in recent years, wherein soybean proteins in the field of vegetable proteins are widely researched due to the characteristics of greenness, environmental protection, renewability and the like. However, natural soy protein is a compact globular structure formed by relatively weak intermolecular forces such as hydrogen bonds, van der waals forces, disulfide bonds, and hydrophobic interactions. Many reactive or non-polar hydrophobic groups are surrounded by the globular structure of proteins and thus do not form strong cross-linked networks of molecules by chemical reactions. Therefore, the traditional soy protein adhesive has poor water resistance and bonding strength and cannot be used as a substitute of aldehyde adhesives.
The spirulina protein is a single-cell protein, has the advantages of wide raw material source, high substrate conversion efficiency, fast growth and reproduction and the like, and is one of important protein sources in the food industry and the feed industry. Meanwhile, the spirulina protein is a natural alga which is propagated in a large area, the protein content is up to 70 percent, and is twice of that of the soybean. The spirulina has very low cellulose content in the cell wall, and the intracellular protein is easy to separate and extract. The novel environment-friendly aldehyde-free adhesive prepared by taking the spirulina protein as the main raw material not only can get rid of dependence on non-renewable resources such as petroleum fossil and the like, but also can make up harmful volatile matters volatilized in the production and use processes of the aldehyde adhesive.
However, there is almost no research on the utilization of spirulina to isolate protein to solve the green and environmental problem of wood adhesives.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a spirulina protein adhesive; the adhesive gets rid of the dependence on non-renewable resources from the source, and overcomes the defects of low bonding strength, poor water resistance and the like of the traditional protein adhesive; meanwhile, the adhesive does not contain harmful volatile substances such as formaldehyde and the like, the harm of aldehyde adhesives to human bodies is greatly reduced, and the adhesive is an environment-friendly and renewable green adhesive.
The invention further aims to provide a preparation method of the spirulina protein adhesive.
The invention also aims to provide an application of the spirulina protein adhesive; the plywood prepared by the adhesive disclosed by the invention has stronger bonding strength and water resistance, and all properties meet the requirements of national relevant standards.
The purpose of the invention is realized by the following technical scheme:
the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 4-10 parts of spirulina protein powder, 40-70 parts of water, 0.1-0.6 part of modifier and 1-8 parts of cross-linking agent.
Preferably, the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 6-8 parts of spirulina protein powder, 45-65 parts of water, 0.2-0.5 part of modifier and 2-6 parts of cross-linking agent.
More preferably, the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 6 parts of spirulina protein powder, 50 parts of water, 0.3 part of modifier and 6 parts of cross-linking agent.
The modifier is more than one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
The cross-linking agent is more than one of ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether.
The preparation method of the spirulina protein adhesive comprises the following steps:
s1, weighing spirulina protein powder, uniformly mixing with water, and then placing at 70 ℃ for continuous stirring;
s2, adding a modifier into the reaction solution, reducing the stirring temperature to 60 ℃, and continuing stirring for 30 min;
s3, adding a cross-linking agent into the reaction liquid, keeping the temperature of the reaction liquid at 60 ℃, and continuously stirring until the reaction is finished to obtain the spirulina protein adhesive.
In the step S1, the spirulina protein powder and water are mixed according to the mass ratio of 1: (6-9) mixing uniformly at room temperature.
In the step S1, the rotating speed of the continuous stirring is set to be 800r/min, and the stirring time is 60 min.
In step S3, the continuous stirring speed is set to 1000r/min, and the stirring time is 60 min.
The spirulina protein adhesive is applied to the field of plywood preparation.
The adhesive prepared by the invention has good adhesive bonding performance, initial adhesion and excellent water resistance, and also has good adhesive bonding performance, initial adhesion and excellent water resistance; the plywood prepared by the adhesive has the bonding strength meeting the requirements of II-type plywood in national standard GB/T9846-2015, and the adhesive is simple in preparation process, low in cost and suitable for actual production and application of artificial boards.
The principle of the invention is as follows:
the protein source material selected by the invention is spirulina protein powder, wherein the content of protein in the spirulina protein powder is as high as 58.5-83.4%, the content of carbohydrate is about 15-20%, the content of active polysaccharide is about 7-8%, and the content of fat and cholesterol is only about 4%. The main substance in the spirulina protein powder is spirulina protein, the protein content is far higher than that in soybean, and the water resistance and the bonding strength of the adhesive prepared by the higher protein content are better than those of the adhesive prepared by the lower protein content. Secondly, the spirulina has relatively high protein content and complete amino acid types, more carried active groups can provide more reaction sites, and chemical reaction is easy to occur in the process of preparing the adhesive.
The modifier selected by the invention is more than one of sodium hydroxide, calcium hydroxide and potassium hydroxide, the protein is a biological macromolecule formed by condensation reaction by taking amino acid as a basic unit, the amino acid forms a peptide chain by dehydration condensation of amino groups and carboxyl groups at two ends of the molecule, the side group of the peptide chain is a large number of active functional groups such as phenolic hydroxyl (Ph-OH), sulfydryl (-SH) and the like, and the peptide chain forms a multi-stage structure of the protein by spiral folding, so that a large number of polar regions are wrapped in the protein and cannot be utilized. Strong base such as sodium hydroxide can effectively enable other chemical bonds such as hydrogen bonds and disulfide bonds connecting peptide chains in protein and weak interaction force to be damaged, partial hydrolysis of protein is caused, the multi-stage structure of the protein is damaged, originally bent, folded and spiral polypeptide chains gradually extend to form a loose peptide chain structure, the folded and spiral peptide chains extend to form a plurality of linear chain structures with amino acid as units and different molecular weights, a large number of active groups on the side groups and the tail ends of the peptide chains are exposed, abundant cross-linking points are provided for further modification reaction, and the peptide chains can be combined with other modifier functional groups in a proper chemical environment, so that a molecular structure with a net structure is formed, and finally a product with adhesive performance is synthesized.
The cross-linking agent selected by the invention is one or more of ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and neopentyl glycol diglycidyl oxide ether, the side chain of a protein molecule contains various active groups (such as amino, carboxyl, sulfydryl, imidazolyl, guanidino, methylthio and the like), and by introducing a chemical cross-linking molecule, protein molecule polypeptide chains can be connected in the curing process by virtue of amino acid active groups, so that a net structure is formed, the acting force among soybean protein molecules is converted from a hydrogen bond to a covalent bond for connection, the structural stability of the adhesive is improved, and the water resistance of the adhesive is further improved. In addition, the small-molecule crosslinking assistant can reduce the viscosity of the adhesive before curing, and is beneficial to sizing the plywood by the adhesive.
Compared with the prior art, the invention has the following advantages and effects:
(1) the preparation method of the spirulina protein adhesive has the advantages of simple process, simple required raw materials, low cost and less required energy consumption.
(2) The protein adhesive overcomes the defects of the traditional protein adhesive in the aspects of bonding strength and water resistance, shows good bonding performance and excellent water resistance, and the plywood prepared by using the protein adhesive meets the relevant requirements of national II-type plywood, thereby being an environment-friendly green artificial board.
(3) The spirulina protein adhesive provided by the invention is a green environment-friendly renewable adhesive, the raw material of the spirulina protein adhesive is derived from renewable biomass resources, a way that chemical products obtained from non-renewable resources such as petroleum fossil and the like are taken as basic raw materials of aldehyde adhesives is avoided, excessive dependence on the chemical products is reduced, and pollution and damage to the natural environment are reduced; and secondly, harmful substances such as formaldehyde and the like which harm human health cannot volatilize in the production and use processes of the adhesive and the artificial board thereof, so that the adhesive is a green and environment-friendly product.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the present invention, unless otherwise specified, all the materials and equipment used are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.2 part; ethylene glycol diglycidyl ether: 6 parts.
Example 2
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.2 part; ethylene glycol diglycidyl ether: 0 part of (A).
Example 3
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.2 part; ethylene glycol diglycidyl ether: and 2 parts.
Example 4
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.2 part; ethylene glycol diglycidyl ether: 8 parts.
Example 5
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.3 part; ethylene glycol diglycidyl ether: 6 parts.
Example 6
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.5 part; ethylene glycol diglycidyl ether: 6 parts.
Example 7
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); sodium hydroxide: 0.7 part; ethylene glycol diglycidyl ether: 6 parts.
Example 8
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 8 parts of a mixture; sodium hydroxide: 0.3 part; dipropylene glycol diglycidyl ether: 4 parts.
Example 9
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); potassium hydroxide: 0.5 part; dipropylene glycol diglycidyl ether: 4 parts.
Example 10
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 4 parts of a mixture; calcium hydroxide: 0.3 part; dipropylene glycol diglycidyl ether: 4 parts.
Example 11
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 8 parts of a mixture; sodium hydroxide: 0.7 part; neopentyl glycol diglycidyl allyl ether: 4 parts.
Example 12
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 4 parts of a mixture; potassium hydroxide: 0.6 part; neopentyl glycol diglycidyl allyl ether: 6 parts.
Example 13
The spirulina protein adhesive comprises the following components in parts by mass: water: 50 parts of a mixture; spirulina protein: 6 parts of (1); calcium hydroxide: 0.3 part; neopentyl glycol diglycidyl allyl ether: 6 parts.
Example 14
The spirulina protein adhesive prepared in examples 1-7 was prepared at a concentration of 180-2The glue application amount of the glue is uniformly coated on the surface of a eucalyptus veneer (2.2mm veneers, three layers are counted, the water content is maintained at about 10-12%), the three layers of veneers are assembled in a criss-cross mode, hot pressing is carried out after the three layers of veneers are placed for 20min at room temperature, and the hot pressing technological parameters are as follows: the hot pressing temperature is 150 ℃, the hot pressing time is 10min, and the hot pressing pressure is 2.0 MPa. And (5) preparing the plywood.
And standing the hot-pressed plate for 24 hours at room temperature for testing a series of performances of the hot-pressed plate. Testing performance indexes such as appearance inspection, free formaldehyde content and the like of the prepared adhesive according to the requirements of a GB/T14074-2017 wood adhesive and a resin inspection method thereof; the prepared plywood is tested for performance indexes such as dry bonding strength, wet bonding strength, formaldehyde emission and the like according to the requirements in the test methods of the physical and chemical properties of the GB/T17657-2013 artificial boards and the decorative artificial boards. As shown in table 1.
TABLE 1 physicochemical Properties of Spirulina adhesive and plywood prepared in examples 1-9
As can be seen from the data in the table, according to the requirement of the GB/T14074-2017 wood adhesive and the resin inspection method thereof on the detection of the formaldehyde emission of the prepared spirulina protein adhesive, no formaldehyde is detected in all the examples, and the adhesive obtained by the preparation method provided by the invention is an aldehyde-free environment-friendly adhesive. Through comparison examples 1-4, the dry and wet bonding strength of the plywood shows the trend of rising first and then falling, the dry and wet bonding strength without the addition of ethylene glycol diglycidyl ether is respectively 1.04MPa and 0.37MPa, the wet bonding strength is lower than the wet strength requirement of national type II plywood, when 2 parts of ethylene glycol diglycidyl ether is added, the wet bonding strength is more than 0.7MPa, the strength requirement is met, and with the addition of 6 parts of ethylene glycol diglycidyl ether, the dry and wet bonding strength respectively reaches 1.45MPa and 1.20 MPa. By comparing examples 1, 5-7, it was found that when 0.2 parts sodium hydroxide was added, the resulting plywood had dry and wet bond strengths of 1.45MPa and 1.20MPa, respectively, and when 0.3 parts sodium hydroxide was added, the dry and wet bond strengths increased to 1.55MPa and 1.31 MPa. The environment-friendly renewable spirulina protein adhesive prepared by the invention is suitable for production equipment and hot pressing process flow required by current plywood preparation, and the production cost is saved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A spirulina protein adhesive is characterized in that: the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 4-10 parts of spirulina protein powder, 40-70 parts of water, 0.1-0.6 part of modifier and 1-8 parts of cross-linking agent.
2. The spirulina protein adhesive according to claim 1, wherein: the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 6-8 parts of spirulina protein powder, 45-65 parts of water, 0.2-0.5 part of modifier and 2-6 parts of cross-linking agent.
3. The spirulina protein adhesive according to claim 1, wherein: the spirulina protein adhesive is prepared from the following raw materials in parts by weight: 6 parts of spirulina protein powder, 50 parts of water, 0.3 part of modifier and 6 parts of cross-linking agent.
4. The spirulina protein adhesive according to claim 1, wherein: the modifier is more than one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
5. The spirulina protein adhesive according to claim 1, wherein: the cross-linking agent is more than one of ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether.
6. The method for preparing a spirulina protein adhesive according to any one of claims 1 to 5, which comprises the following steps:
s1, weighing spirulina protein powder, uniformly mixing with water, and then placing at 70 ℃ for continuous stirring;
s2, adding a modifier into the reaction solution, reducing the stirring temperature to 60 ℃, and continuing stirring for 30 min;
s3, adding a cross-linking agent into the reaction liquid, keeping the temperature of the reaction liquid at 60 ℃, and continuously stirring until the reaction is finished to obtain the spirulina protein adhesive.
7. The method for preparing the spirulina protein adhesive according to claim 6, wherein the method comprises the following steps: in the step S1, the spirulina protein powder and water are mixed according to the mass ratio of 1: (6-9) mixing uniformly at room temperature.
8. The method for preparing the spirulina protein adhesive according to claim 6, wherein the method comprises the following steps: in the step S1, the rotating speed of the continuous stirring is set to be 800r/min, and the stirring time is 60 min.
9. The method for preparing the spirulina protein adhesive according to claim 6, wherein the method comprises the following steps: in step S3, the continuous stirring speed is set to 1000r/min, and the stirring time is 60 min.
10. Use of a spirulina protein adhesive according to any one of claims 1-5 in the field of plywood production.
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