CN116445128A - Cellulose reinforced protein adhesive loaded with metal ions and preparation method thereof - Google Patents
Cellulose reinforced protein adhesive loaded with metal ions and preparation method thereof Download PDFInfo
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- CN116445128A CN116445128A CN202211192622.XA CN202211192622A CN116445128A CN 116445128 A CN116445128 A CN 116445128A CN 202211192622 A CN202211192622 A CN 202211192622A CN 116445128 A CN116445128 A CN 116445128A
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- cellulose
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- metal ions
- protein adhesive
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 128
- 239000000853 adhesive Substances 0.000 title claims abstract description 126
- 229920002678 cellulose Polymers 0.000 title claims abstract description 101
- 239000001913 cellulose Substances 0.000 title claims abstract description 101
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 63
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 59
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 60
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 60
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 60
- 235000020232 peanut Nutrition 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011701 zinc Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 43
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000012054 meals Nutrition 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004246 zinc acetate Substances 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 241001553178 Arachis glabrata Species 0.000 claims abstract 15
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 6
- 229960002218 sodium chlorite Drugs 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 244000105624 Arachis hypogaea Species 0.000 description 45
- 235000018102 proteins Nutrition 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 33
- 241000219000 Populus Species 0.000 description 13
- 150000001299 aldehydes Chemical class 0.000 description 13
- 239000011120 plywood Substances 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 5
- 238000007037 hydroformylation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 108010080379 Fibrin Tissue Adhesive Proteins 0.000 description 2
- 108010064851 Plant Proteins Proteins 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000021118 plant-derived protein Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229930195730 Aflatoxin Natural products 0.000 description 1
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229940006486 zinc cation Drugs 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
-
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a cellulose reinforced protein adhesive loaded with metal ions, which comprises the following steps: uniformly dispersing aldehyde cellulose in water, stirring, adding polyethyleneimine, reacting at 40-60 ℃ for 1.5-2.5 hours, and treating after the reaction is finished to obtain the amino cellulose; preparing a mixed solution containing zinc acetate as a zinc source and silver nitrate as a silver source, adding the aminated cellulose fiber under stirring, reacting for 1.5-2.5 hours at 65-75 ℃, and treating after the reaction is finished to obtain cellulose loaded with metal ions; and thirdly, mixing the cellulose loaded with metal ions, the high-temperature peanut meal and the polyamide epichlorohydrin under stirring to prepare the protein adhesive. Cellulose-reinforced protein adhesive loaded with metal ions. The invention has the beneficial effects of enhancing the strength and the water resistance of the protein adhesive.
Description
Technical Field
The invention relates to the technical field of adhesive preparation. More particularly, the invention relates to a cellulose reinforced protein adhesive loaded with metal ions and a preparation method thereof.
Background
The usage amount of the adhesive (melamine formaldehyde adhesive, phenolic resin adhesive and urea formaldehyde resin adhesive) based on petroleum resources is more than 90% in the plywood industry in China, formaldehyde and free phenol can be released in the preparation, transportation and use processes, and the adhesive is harmful to human bodies and pollutes the environment. With the exhaustion of petroleum resources and the attention of people to environmental protection, the vegetable protein adhesive is a potential substitute of 'trialdehyde glue' because the raw materials of the vegetable protein adhesive are renewable, nontoxic and harmless.
In recent years, the annual output of high-temperature peanut meal in China exceeds 400 ten thousand tons, and the high-temperature peanut meal is a byproduct after high-temperature oil extraction of peanut kernels, has the protein content of more than 45 percent and is a good vegetable protein raw material. However, the limit value (less than or equal to 50 ppb) of aflatoxin in peanut meal in the feed sanitation standard (GB 13078-2017 feed sanitation standard) stipulates that most of high-temperature peanut meal cannot be used in the feed industry but can only be used as waste, so that the high-temperature peanut meal protein adhesive can be developed. However, the high-temperature peanut meal adhesive has the problems of low bonding strength, poor water resistance and poor antibacterial property, and good flame retardance is also indispensable when the high-temperature peanut meal adhesive is applied to public places.
The application number is 2021115380287, a method for increasing the strength of the protein adhesive by adding aldehyde cellulose is disclosed in a patent with the name of a plant protein adhesive, a preparation method and application of the plant protein adhesive, and how to further improve the positive influence of the aldehyde cellulose on the strength and the water resistance of the protein adhesive and endow the adhesive with excellent antibacterial property and flame retardance is a problem which needs to be solved urgently at present.
Disclosure of Invention
It is an object of the present invention to solve at least the above problems and to provide at least the advantages to be described later.
The invention also aims to provide a preparation method of the cellulose reinforced protein adhesive loaded with metal ions, wherein the metal ions are loaded on the surface of peanut shell cellulose, the metal ions are used as reinforcing phases to improve the bonding strength and the water resistance of the adhesive, and the adhesive is endowed with excellent antibacterial property and flame retardance.
It is still another object of the present invention to provide a metal ion-loaded cellulose-reinforced protein adhesive having excellent adhesive strength, water resistance, antibacterial properties and flame retardancy.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a cellulose-reinforced protein adhesive loaded with metal ions, comprising the steps of:
uniformly dispersing the aldehyde cellulose in water, regulating the pH value to 7.5-8.5, stirring, adding polyethylenimine accounting for 2-4% of the aldehyde cellulose, reacting at 40-60 ℃ for 1.5-2.5 hours, and treating after the reaction is finished to obtain the amino cellulose;
preparing a mixed solution containing zinc acetate as a zinc source and silver nitrate as a silver source, adding the amino cellulose fiber under stirring, reacting for 1.5-2.5 hours at 65-75 ℃, and treating to obtain cellulose loaded with metal ions after the reaction is finished;
and thirdly, stirring and mixing the cellulose loaded with the metal ions and the high-temperature peanut meal powder to obtain the protein adhesive.
Preferably, the preparation method of the aldehyde cellulose comprises the following steps:
uniformly dispersing peanut shell cellulose in water, regulating the pH to 2.5-3.5, sequentially adding sodium periodate and isopropanol, controlling the temperature to be 30-60 ℃, reacting for 3-6 hours, and treating to obtain aldehyde cellulose, wherein the whole reaction device is placed in a dark environment during the reaction, and the mass-volume ratio of the peanut shell cellulose to the water to the sodium periodate to the isopropanol is 1g:100mL:2.2-2.4g:0.05-0.07g.
Preferably, the treatment in the treatment to obtain the aldehyde cellulose is specifically: cooling the reaction liquid to room temperature, adding glycol, stirring, repeatedly washing with deionized water to neutrality, filtering, and drying, wherein the mass volume ratio of peanut shell cellulose to glycol is 3g:10mL.
Preferably, the preparation method of the peanut shell cellulose comprises the following steps:
crushing peanut shells to 200 meshes, immersing the peanut shells in a sodium hydroxide solution with the mass fraction of 2%, stirring the mixture for 2.5 to 3.5 hours at the temperature of 75 to 85 ℃, repeatedly cleaning the mixture to be neutral, and airing the mixture to obtain alkali-soaked peanut shells, wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:20;
placing the alkali-soaked peanut shells into sodium chlorite solution with the mass volume fraction of 1.7%, regulating the pH value of the solution to 4-5 by glacial acetic acid, controlling the temperature to 75-80 ℃, washing and filtering for several times after reacting for 3.5-4.5 hours until the pH value of the filtrate reaches neutrality, and airing to obtain peanut shell cellulose, wherein the feed liquid ratio of the alkali-soaked peanut shells to the sodium chlorite solution is 1g:20mL.
Preferably, in the first step, the feed liquid ratio of the aldehyde cellulose to the water is 1g:100mL.
Preferably, in the second step, the zinc acetate is used as a zinc source and the silver nitrate is used as a silver source to prepare a mixed solution comprising the zinc acetate and the silver nitrate, which specifically comprises the following steps:
according to the feed liquid ratio of 0.11g:50mL, weighing zinc acetate dihydrate water solution to prepare zinc acetate solution;
a0.5 mmol/L silver nitrate solution was prepared, and then a zinc acetate solution was mixed with the silver nitrate solution in equal volumes.
Preferably, the step S3 specifically includes:
adding half of the cellulose loaded with metal ions into deionized water, stirring for 14-16min, adding high-temperature peanut meal, stirring for 8-12min, and continuously adding the rest half of the cellulose loaded with metal ions, stirring for 14-16min to obtain the protein adhesive, wherein the mass of the cellulose loaded with metal ions, water, high-temperature peanut meal and polyamide epichlorohydrin is 3-4:150:50:5.
preferably, the stirring is carried out for 14-16min, and then the polyamide epichlorohydrin is added and stirred for 25-35min.
Preferably, the method further comprises the steps of: ultrasonic treatment is carried out for 30-50min at 250kw/20 KHz.
The fibrin adhesive is prepared by the preparation method of the cellulose enhanced fibrin adhesive loaded with metal ions.
The invention at least comprises the following beneficial effects:
the first hydroformylation peanut shell cellulose is synchronously loaded with Zn after amination 2+ 、Ag + The metal ions are used as the reinforcing phase for preparing the adhesive, compared with the aldehyde-formed peanut shell cellulose, the adhesive bonding strength and water resistance of the adhesive can be effectively enhanced, and the adhesive is endowed with excellent antibacterial property and flame retardance, and the adhesive is specific: compared with the aldehyde cellulose, the dry bonding strength is improved by 31.6%, the wet (63 ℃) bonding strength is improved by 26.9%, the wet (100 ℃) bonding strength is improved by 33.3%, the mass loss is reduced from 33.57% to 21.45%, the mildew-proof time is increased by 196%, and the flame retardance is increased by 64.1%;
secondly, in the preparation process, ag/Zn@DAPF is added step by step before and after, so that the uniformity of mixing with high-temperature peanut meal powder is improved, the aggregation probability is reduced, and the bonding strength, water resistance, antibacterial property and flame retardance of the adhesive are synchronously improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a diagram of the reaction mechanism of the present invention;
FIG. 2 is a schematic structural diagram of the effect of different addition amounts of Ag/Zn@DAPF on the bonding strength of the high-temperature peanut meal adhesive;
fig. 3 is a schematic structural diagram of the effect of different ultrasound times on the glue strength.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
Example 1 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions comprises the following steps:
s1, preparation of peanut shell cellulose
Washing peanut shells, airing, crushing the aired peanut shells to 200 meshes, immersing the peanut shells in a sodium hydroxide solution with the mass fraction of 2%, stirring the mixture for 3 hours at 80 ℃, repeatedly washing the peanut shells to be neutral by using deionized water, and airing to obtain alkali-soaked peanut shells, wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:20;
the alkali soaked peanut shells were placed in 1.7% (m/V) sodium chlorite (NaClO) 2 ) Adjusting the pH of the solution to 4.5 by glacial acetic acid, continuously stirring the solution in a constant-temperature water bath at 80 ℃ by using a magnetic stirrer, filtering for a plurality of times after reacting for 4 hours until the pH of the filtrate reaches neutral, and naturally airing to obtain peanut shell cellulose, wherein the feed liquid ratio of the alkali-soaked peanut shell to the sodium chlorite solution is 1:20 (g/mL);
s2, preparation of aldehyde cellulose
Weighing 30g of peanut shell cellulose, uniformly dispersing in 3000mL of deionized water, placing in a conical flask, and adjusting the pH to 3;
weighing 69g of sodium periodate and 1.8g of isopropanol, respectively adding into the reaction system, reacting for 3-6 hours in a water bath kettle with the temperature of 30-60 ℃, then standing to normal temperature, adding 100ml of ethylene glycol to remove redundant sodium periodate, repeatedly washing with deionized water to be neutral to obtain cellulose aldehyde, drying and then preserving for later use, wherein the whole reaction device is placed in a dark environment during the reaction;
s3, preparation of amino cellulose
Uniformly dispersing 20g of formylated cellulose in 2000mL of water, regulating the pH value of the system to 8.0 by using 0.1mol/L NaOH, adding 0.6g of Polyethyleneimine (PEI) under the action of slow magnetic stirring, controlling the reaction system to react for 2 hours at the temperature of 40-60 ℃ by using water bath, repeatedly washing with deionized water for many times after the reaction is finished until the washing liquid is neutral, and obtaining the aminated cellulose for standby, wherein the water is deionized water;
s3, preparation of metal ion loaded cellulose
Preparing a sample by taking zinc acetate as a zinc source and silver nitrate as a silver source and taking amino cellulose as a carrier, wherein the sample comprises the following concrete steps:
22g of zinc acetate dihydrate was dissolved in 10L of the aqueous solution to obtain zinc acetate (Zn (CH 3 COO) 2 ) Mixing 10mL of 0.5mmol/L silver nitrate solution, adding 20g of aminated cellulose fiber under rapid magnetic stirring, controlling the solution to react for 2 hours at the reaction temperature of 70 ℃, washing off unsupported nano particles with deionized water after the solution is finished, and then drying at constant temperature for 4 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain cellulose (Ag/Zn@DAPF) loaded with metal ions;
s4, preparation of protein adhesive
S41, adding 4g of Ag/Zn@DAPF into 300g of deionized water, stirring for 15min, and adding 100g of high-temperature peanut meal powder (200 meshes) and stirring for 10min;
s42, continuously adding 4g of Ag/Zn@DAPF and stirring for 15min;
s43, then carrying out ultrasonic treatment at 250kw/20KHz for 30min, adding 10g of polyamide epichlorohydrin (PAE), and stirring for 30min to obtain the protein adhesive.
Example 2 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the amount of Ag/Zn@DAPF added in the step S41 is 1g;
the amount of Ag/Zn@DAPF added in step S42 was 1g.
Example 3 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the amount of Ag/Zn@DAPF added in the step S41 is 2g;
the amount of Ag/Zn@DAPF added in step S42 was 2g.
Example 4 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the amount of Ag/Zn@DAPF added in the step S41 is 3g;
the amount of Ag/Zn@DAPF added in step S42 was 3g.
Example 5 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the amount of Ag/Zn@DAPF added in the step S41 is 5g;
the amount of Ag/Zn@DAPF added in step S42 was 5g.
Example 6 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
no ultrasonic treatment is performed in step S43.
Example 7 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the sonication time in step S43 was 10min.
Example 8 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the sonication time in step S43 was 20min.
Example 9 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the ultrasonic treatment time in step S43 is 40min.
Example 10 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is the same as in example 1, except that:
the sonication time in step S43 was 50min.
Example 11 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions comprises the following steps:
adding 8g of Ag/Zn@DAPF into 300g of deionized water, stirring for 15min, and adding 100g of high-temperature peanut meal powder (200 meshes), stirring for 25min to obtain the adhesive, wherein the preparation method of the Ag/Zn@DAPF is the same as in example 1.
Example 12 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions comprises the following steps:
adding 8g of Ag/Zn@DAPF into 300g of deionized water, stirring for 15min, adding 100g of high-temperature peanut meal powder (200 meshes), stirring for 25min, and performing ultrasonic treatment at 250kw/20KHz for 40min to obtain the adhesive.
Example 13 ]
The preparation method of the cellulose reinforced protein adhesive loaded with metal ions comprises the following steps:
adding 8g of Ag/Zn@DAPF into 300g of deionized water, stirring for 15min, adding 100g of high-temperature peanut meal (200 meshes), stirring for 25min, performing ultrasonic treatment at 250kw/20KHz for 40min, adding 10g of polyamide epichlorohydrin (PAE), and stirring for 30min to obtain the series adhesive.
Comparative example 1 ]
The preparation method of the adhesive comprises the following steps:
adding 4g of cellulose aldehyde group into 300g of deionized water, stirring for 15min, adding 100g of high-temperature peanut meal (200 meshes), stirring for 10min, continuously adding 4g of cellulose aldehyde group, stirring for 15min, performing ultrasonic treatment at 250kw/20KHz for 40min, adding 10g of polyamide epichlorohydrin (PAE), and stirring for 30min to obtain a series of adhesives, wherein the preparation method of the cellulose aldehyde group is the same as that of example 1.
Comparative example 2 ]
The preparation method of the adhesive comprises the following steps:
adding 4g of amino cellulose into 300g of deionized water, stirring for 15min, adding 100g of high-temperature peanut meal (200 meshes), stirring for 10min, continuously adding 4g of amino cellulose, stirring for 15min, performing ultrasonic treatment at 250kw/20KHz for 40min, adding 10g of polyamide epichlorohydrin (PAE), and stirring for 30min to obtain the series adhesive, wherein the preparation method of the amino cellulose is the same as that of the example 1.
Comparative example 3 ]
The preparation method of the adhesive comprises the following steps:
the difference from example 1 is that the preparation method of the metal ion loaded cellulose is different, specifically:
22g of zinc acetate dihydrate was dissolved in 20L of the aqueous solution to obtain zinc acetate (Zn (CH 3 COO) 2 ) And adding 20g of aminated cellulose fiber under rapid magnetic stirring, controlling the solution to react for 2 hours at the reaction temperature of 70 ℃, washing off the unsupported nano particles with deionized water after the reaction is finished, and then drying at constant temperature for 4 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the cellulose (Zn@DAPF) loaded with metal ions.
Comparative example 4 ]
The preparation method of the adhesive comprises the following steps:
the difference from example 1 is that the preparation method of the metal ion loaded cellulose is different, specifically:
preparing 20L of 0.25mmol/L silver nitrate solution, adding 20g of aminated cellulose fiber under rapid magnetic stirring, controlling the solution to react for 2 hours at the reaction temperature of 70 ℃, washing off unsupported nano particles with deionized water after the solution is finished, and then drying for 4 hours at constant temperature in a vacuum drying oven at the temperature of 80 ℃ to obtain cellulose (Ag@DAPF) loaded with metal ions.
Performance detection
1. Preparation of three-layer poplar plywood
The adhesive is respectively smeared on the opposite sides of the 3 poplar veneers, and the smearing amount of each layer of adhesive is 180g/m 2 ；
Prepressing after every two vertical assembling of 3 poplar veneer lines, wherein the prepressing temperature is as follows: 25 ℃, prepressing pressure: 1-1.2 MPa, pre-pressing time: 10min, hot pressing the pre-pressed wood at the hot pressing temperature: 120 ℃, hot pressing time: 70s/mm, hot-pressing pressure: 1.2MPa, obtaining three-layer poplar plywood;
wherein, before the poplar veneer is reused, the poplar veneer is dried until the moisture content is 10 percent, the drying temperature is 40 ℃, and the wind speed is 10m/s.
2. Influence of Ag/Zn@DAPF addition on adhesive properties
2.1 taking the protein adhesives prepared in the examples 1-5 as adhesives to respectively prepare corresponding three-layer poplar plywood according to the preparation method of the three-layer poplar plywood described in the section < one >;
2.2 the glue strength was measured according to GB/T9846-2015 and the result is shown in FIG. 2, wherein the addition amount of Ag/Zn@DAPF for example 2 was 2%, the addition amount of Ag/Zn@DAPF for example 3 was 4%, the addition amount of Ag/Zn@DAPF for example 4 was 6%, the addition amount of Ag/Zn@DAPF for example 1 was 8%, and the addition amount of Ag/Zn@DAPF for example 5 was 10%.
As can be seen from fig. 2, as the addition amount of Ag/zn@dapf increases, the adhesive strength of the prepared protein adhesive tends to increase and decrease, wherein when the addition amount of Ag/zn@dapf is 8%, the adhesive strength of the corresponding protein adhesive is highest, the adhesive strength in a dry state is 2.34MPa, the adhesive strength in a wet state (63 ℃) is 1.57MPa, and the adhesive strength in a wet state (100 ℃) is 1.34MPa.
3. Influence of ultrasonic time on adhesive properties
3.1 taking the protein adhesives prepared in examples 6-10 as adhesives to respectively prepare corresponding three-layer poplar plywood according to the preparation method of the three-layer poplar plywood described in < one >;
3.2 the glue strength was measured according to GB/T9846-2015 and the results are shown in FIG. 3:
as can be seen from fig. 3, the adhesive strength of the prepared protein adhesive tends to increase and decrease with increasing ultrasonic time, wherein the adhesive strength of the corresponding protein adhesive is highest when the ultrasonic time is 40min, the adhesive strength in dry state is 2.41MPa, the adhesive strength in wet state (63 ℃) is 1.62MPa, and the adhesive strength in wet state (100 ℃) is 1.46MPa.
4. Performance detection of protein adhesive
4.1, glue Strength detection
Taking the protein adhesives prepared in comparative examples 1-4, example 9 and examples 11-13 as adhesives, and respectively preparing corresponding three-layer poplar plywood according to the preparation method of the three-layer poplar plywood described in < one >;
the bond strength of each three-layer poplar plywood was measured according to GB/T9846-2015 and the formaldehyde release was measured as shown in Table 1:
table 1 glue strength of three-ply plywood product
As can be seen from table 1:
(1) the dry bond strength, wet (63 ℃ C.) bond strength, wet (100 ℃ C.) bond strength of example 9 are all superior to those of comparative examples 1 and 2, demonstrating that the hydroformylation cellulose is synchronously loaded with Zn after amination 2+ 、Ag + The bonding strength of the adhesive can be effectively improved after metal ions, wherein the bonding strength of the adhesive in a dry state is improved by 31.6 percent, the bonding strength in a wet state (63 ℃) is improved by 26.9 percent, and the bonding strength in a wet state (100 ℃) is improved by 33.3 percent compared with that in comparative example 1;
(2) the dry bonding strength, wet (63 ℃) bonding strength and wet (100 ℃) bonding strength of the example 9 are all superior to those of the comparative example 3 and the comparative example 4, which show that the formylated cellulose is synchronously loaded with Zn 2+ 、Ag + After metal ion, relative to single-load Zn 2+ 、Ag + The bonding strength of the adhesive can be improved by being matched with the adhesive;
(3) the bonding strength of the example 12 is superior to that of the example 11, which shows that the ultrasonic treatment can enhance the crosslinking effect among materials and improve the bonding strength of the adhesive; the bond strength of example 13 is superior to example 12, demonstrating that the addition of PAE crosslinker can improve the bond strength of the adhesive; the bond strength of example 9 is superior to example 13, demonstrating that the bond strength of the adhesive can be improved by the stepwise addition of Ag/zn@dapf, before and after, relative to the high temperature peanut meal, avoiding aggregation.
4.2 Water resistance detection
Quantitatively taking the protein adhesives prepared in comparative examples 1-4, example 9 and examples 11-13, respectively, and placing in an oven at 130deg.C to constant weight (M j ) Then, the constant weight cured protein binder sample was immersed in water at room temperature for 48 hours and at 105℃under constant weight (M i ) The mass loss (%) = [ (M) of each protein adhesive was calculated j -M i )/M j ]*100% and the specific results are shown in table 2 below:
TABLE 2 Mass loss of protein adhesives
| Sample of | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Loss of mass (%) | 33.57 | 32.16 | 31.27 | 26.41 |
| Sample of | Example 11 | Example 12 | Example 13 | Example 9 |
| Loss of mass (%) | 37.71 | 33.23 | 31.98 | 21.45 |
Note that: the higher the mass loss, the poorer the water resistance.
As is clear from Table 2, example 9 has water resistance superior to that of comparative examples 1 and 2, and shows that the cellulose aldehyde group is synchronously loaded with Zn after amination 2+ 、Ag + The water resistance of the adhesive can be effectively improved after metal ions;
further, example 9 has water resistance superior to that of comparative example 3 and comparative example 4, showing that the cellulose aldehyde is subjected to Zn simultaneous loading 2+ 、Ag + After metal ion, relative to single-load Zn 2+ 、Ag + The water resistance of the adhesive can be improved by being matched with the adhesive;
furthermore, the bond strength of example 12 is better than that of example 11, the bond strength of example 13 is better than that of example 12, and the bond strength of example 9 is better than that of example 13, indicating that the water resistance of the adhesive can be improved by ultrasonic treatment, addition of PAE cross-linking agent, and treatment of adding Ag/Zn@DAPF step by step before and after.
4.3 mildew-proof time detection
20g of the protein adhesives prepared in comparative examples 1-4, example 9 and examples 11-13 are respectively placed in sterilized petri dishes, placed in a constant temperature and humidity box, the temperature in the box is controlled to be 37 ℃ and the humidity is controlled to be 98%, observed until mold appears, and recorded, and specific results are shown in table 3:
TABLE 3 mildew time of adhesives
| Sample of | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Mildew proof time (Tian) | 24 | 26 | 49 | 56 |
| Sample of | Example 11 | Example 12 | Example 13 | Example 9 |
| Mildew proof time (Tian) | 27 | 28 | 68 | 71 |
As is clear from Table 3, the mildew-proof time of example 9 is superior to that of comparative examples 1 and 2, and it is demonstrated that the cellulose aldehyde is synchronously loaded with Zn after amination 2+ 、Ag + The mildew-proof time of the adhesive can be effectively improved after metal ions;
further, the mildew-proof time of example 9 is better than that of comparative example 3 and comparative example 4, demonstrating that the cellulose hydroformylation is synchronously loaded with Zn 2+ 、Ag + Metal ion rear relative to singleZn-loaded 2+ 、Ag + The mildew-proof time of the adhesive can be improved in a matched mode;
furthermore, the bond strength of example 12 is better than that of example 11, the bond strength of example 13 is better than that of example 12, and the bond strength of example 9 is better than that of example 13, which indicates that the mildew-proof time of the adhesive can be improved by ultrasonic treatment, addition of PAE cross-linking agent, and treatment of adding Ag/Zn@DAPF step by step before and after.
4.4 flame retardant time detection
Quantitatively taking the protein adhesives prepared in comparative examples 1-4, example 9 and examples 11-13, and curing the protein adhesives under constant weight at 105 ℃ to obtain sheet-shaped cured adhesives;
clamping the sheet-shaped cured adhesive by forceps, and placing a cotton ball on the top end of the sheet-shaped cured adhesive sample;
igniting the alcohol lamp, placing the flaky cured adhesive with cotton above the alcohol lamp, observing the ignition time of the cotton, and determining the ignition time as the flame retardant time corresponding to the protein adhesive, wherein the specific results are shown in the following table 4:
TABLE 4 flame retardant time
| Sample of | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Flame retardant time (seconds) | 64 | 68 | 98 | 87 |
| Sample of | Example 11 | Example 12 | Example 13 | Example 19 |
| Flame retardant time (seconds) | 79 | 83 | 103 | 105 |
As is clear from Table 4, the flame retardant time of example 9 is superior to that of comparative examples 1 and 2, demonstrating that the hydroformylation cellulose is synchronously loaded with Zn after amination 2+ 、Ag + The flame retardant time of the adhesive can be effectively improved after metal ions;
further, the flame retardant time of example 9 is better than that of comparative example 3 and comparative example 4, demonstrating that the cellulose hydroformylation is Zn-loaded synchronously 2+ 、Ag + After metal ion, relative to single-load Zn 2+ 、Ag + The flame retardant time of the adhesive can be improved in a matched mode;
furthermore, the bond strength of example 12 is better than that of example 11, the bond strength of example 13 is better than that of example 12, and the bond strength of example 9 is better than that of example 13, indicating that the flame retardant time of the adhesive can be improved by ultrasonic treatment, addition of PAE cross-linking agent, and treatment of adding Ag/Zn@DAPF step by step before and after.
5. Reaction mechanism: as shown in fig. 1, in the process of carrying out metal ion loading, zinc acetate solute is dispersed in an aqueous solution containing a certain mass of aminated fiber, and zinc acetate is dissolved and converted into zinc cation (Zn 2+ ) Amino groups immediately bound to the molecular chain of the aminated cellulose fiberThe group forms coordination bond, then zinc ion reacts with hydroxide radical in solution immediately under alkaline condition to generate zinc hydroxide, the solution is heated at a certain temperature, the zinc hydroxide is dehydrated, and finally slowly nucleates and gradually converts into ZnO nano-particles, and the ZnO nano-particles are adsorbed on the surface of cellulose fiber through covalent bond under the coordination effect of amino and metal.
During the metal ion loading process, ag + Binding to the fibers by coordination with amino groups, followed by reduction of Ag by aldehyde groups on the fibers + The Ag nano particles are reduced to be in-situ loaded on the surface of the fiber.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (10)
1. The preparation method of the cellulose reinforced protein adhesive loaded with metal ions is characterized by comprising the following steps of:
uniformly dispersing the aldehyde cellulose in water, regulating the pH value to 7.5-8.5, stirring, adding polyethylenimine accounting for 2-4% of the aldehyde cellulose, reacting at 40-60 ℃ for 1.5-2.5 hours, and treating after the reaction is finished to obtain the amino cellulose;
preparing a mixed solution containing zinc acetate as a zinc source and silver nitrate as a silver source, adding the amino cellulose fiber under stirring, reacting for 1.5-2.5 hours at 65-75 ℃, and treating to obtain cellulose loaded with metal ions after the reaction is finished;
and thirdly, stirring and mixing the cellulose loaded with the metal ions and the high-temperature peanut meal powder to obtain the protein adhesive.
2. The method for preparing the cellulose reinforced protein adhesive loaded with metal ions according to claim 1, wherein the method for preparing the aldehyde-modified cellulose is as follows:
uniformly dispersing peanut shell cellulose in water, regulating the pH to 2.5-3.5, sequentially adding sodium periodate and isopropanol, controlling the temperature to be 30-60 ℃, reacting for 3-6 hours, and treating to obtain aldehyde cellulose, wherein the whole reaction device is placed in a dark environment during the reaction, and the mass-volume ratio of the peanut shell cellulose to the water to the sodium periodate to the isopropanol is 1g:100mL:2.2-2.4g:0.05-0.07g.
3. The method for preparing the cellulose reinforced protein adhesive loaded with metal ions according to claim 2, wherein the treatment in the process for obtaining the aldehyde-modified cellulose is specifically as follows: cooling the reaction liquid to room temperature, adding glycol, stirring, repeatedly washing with deionized water to neutrality, filtering, and drying, wherein the mass volume ratio of peanut shell cellulose to glycol is 3g:10mL.
4. The method for preparing the cellulose reinforced protein adhesive loaded with metal ions according to claim 2, wherein the method for preparing the peanut shell cellulose is as follows:
crushing peanut shells to 200 meshes, immersing the peanut shells in a sodium hydroxide solution with the mass fraction of 2%, stirring the mixture for 2.5 to 3.5 hours at the temperature of 75 to 85 ℃, repeatedly cleaning the mixture to be neutral, and airing the mixture to obtain alkali-soaked peanut shells, wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:20;
placing the alkali-soaked peanut shells into sodium chlorite solution with the mass volume fraction of 1.7%, regulating the pH value of the solution to 4-5 by glacial acetic acid, controlling the temperature to 75-80 ℃, washing and filtering for several times after reacting for 3.5-4.5 hours until the pH value of the filtrate reaches neutrality, and airing to obtain peanut shell cellulose, wherein the feed liquid ratio of the alkali-soaked peanut shells to the sodium chlorite solution is 1g:20mL.
5. A method for preparing a metal ion loaded cellulose reinforced protein adhesive according to claim 3, wherein in step one, the feed liquid ratio of the aldehyde-modified cellulose to water is 1g:100mL.
6. The preparation method of the cellulose reinforced protein adhesive loaded with metal ions as claimed in claim 1, wherein in the second step, the zinc acetate is used as a zinc source and the silver nitrate is used as a silver source to prepare a mixed solution comprising the zinc acetate and the silver nitrate, which is specifically as follows:
according to the feed liquid ratio of 0.11g:50mL, weighing zinc acetate dihydrate water solution to prepare zinc acetate solution;
a0.5 mmol/L silver nitrate solution was prepared, and then a zinc acetate solution was mixed with the silver nitrate solution in equal volumes.
7. The method for preparing the cellulose-reinforced protein adhesive loaded with metal ions according to claim 1, wherein the step S3 is specifically:
adding half of the cellulose loaded with metal ions into deionized water, stirring for 14-16min, adding high-temperature peanut meal, stirring for 8-12min, and continuously adding the rest half of the cellulose loaded with metal ions, stirring for 14-16min to obtain the protein adhesive, wherein the mass of the cellulose loaded with metal ions, water, high-temperature peanut meal and polyamide epichlorohydrin is 3-4:150:50:5.
8. the method for preparing the cellulose reinforced protein adhesive loaded with metal ions according to claim 7, wherein the method further comprises adding polyamide epichlorohydrin and stirring for 25-35min after stirring for 14-16 min.
9. The method for preparing a cellulose reinforced protein adhesive loaded with metal ions according to claim 8, wherein the method further comprises the following steps before adding the polyamide epichlorohydrin: ultrasonic treatment is carried out for 30-50min at 250kw/20 KHz.
10. A protein adhesive prepared by the method for preparing a metal ion-loaded cellulose-reinforced protein adhesive according to any one of claims 1 to 9.
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