CN105885772A - Soybean protein biomass non-formaldehyde adhesive and preparation method thereof - Google Patents
Soybean protein biomass non-formaldehyde adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN105885772A CN105885772A CN201610498282.1A CN201610498282A CN105885772A CN 105885772 A CN105885772 A CN 105885772A CN 201610498282 A CN201610498282 A CN 201610498282A CN 105885772 A CN105885772 A CN 105885772A
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- China
- Prior art keywords
- parts
- soybean
- free glue
- soybean protein
- aldehyde
- Prior art date
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- 239000000693 micelle Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229960000490 permethrin Drugs 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000013597 soy food Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a soybean protein biomass non-formaldehyde adhesive which is characterized by comprising the following raw materials: water, soybean protein, alkali, silicate, a surfactant, polyamide polyamine epoxy chloropropane resin, and a compound of the structural formula (I). As soybean protein is subjected to modification treatment, the soybean protein biomass non-formaldehyde adhesive with excellent water-resistant bonding strength can be prepared.
Description
Technical Field
The invention relates to an adhesive and a preparation method thereof, in particular to an aldehyde-free adhesive and a preparation method thereof.
Background
Yield of artificial board 883558m in 20163The demand of the adhesive in China is rapidly increased, the average annual growth rate is about 20% over 10 years, wherein the three-aldehyde adhesive, namely urea formaldehyde, phenol formaldehyde and melamine formaldehyde resin adhesive, is about 600 ten thousand tons, the yield is the maximum, and the three-aldehyde adhesive accounts for about 40% of the total yield of the adhesive. Although the production level of the artificial board adhesive in China is greatly improved and the environmental protection characteristics of the artificial board and the artificial board product are greatly improved after years of efforts, the artificial board and the artificial board product produced by many enterprises, such as furniture, wood floors, indoor wood decorative materials and the like, still have a relatively serious formaldehyde release problem and are a main source of formaldehyde pollution in indoor air pollution. At present, the method for reducing the formaldehyde emission of the artificial board comprises the following steps: modifying a urea-formaldehyde resin adhesive by adopting a low molar ratio; other environment-friendly adhesives are adopted; adding a formaldehyde catching agent into a urea-formaldehyde resin adhesive for the artificial board; post-processing the artificial board. However, these techniques have many disadvantages, such as reduced bonding strength, water resistance and stability, and cannot meet the requirements of use; the curing time is prolonged, and the production efficiency is reduced; greatly increasing the production cost and reducing the product competitiveness. In the face of environmental pollution, non-regenerability of petroleum resources and constant rising dilemma of petrochemical product price, the development of environment-friendly adhesives by using low-price renewable resources becomes an urgent task for upgrading the wood industry again.
The soybean protein adhesive is widely noticed, the soybean protein has the advantages of wide source, strong reproducibility, high reaction activity and the like, and the scholars apply for the soybean protein-based adhesive as early as 1923. However, the soybean protein adhesive has poor water resistance as compared with most synthetic resin adhesives because most proteins are hydrophilic substances and hydrogen bonds are easily broken in a wet state, so that the hydrogen bond bonding formed between the soybean protein and the wood interface can only produce good dry strength, while the wet strength is poor. The adhesive has a limited range of application due to its weak bonding strength and high production cost. Therefore, the soybean protein needs to be modified by improving the existing soybean protein-based adhesive, so that the soybean protein has strong water resistance and bonding strength.
Disclosure of Invention
The invention obtains the soybean protein biomass formaldehyde-free glue with excellent water-resistant bonding strength by modifying the soybean protein.
The invention provides a soybean protein biomass formaldehyde-free glue, which at least comprises the following raw materials: water, soy protein, alkali, silicate, surfactant, polyamide polyamine epichlorohydrin resin and a compound shown in a structural formula (1);
wherein R is1、R2、R3、R4、R5Each independently may be hydrogen or fluorine, and R1、R2、R3、R4、R5Not both may be hydrogen.
In one embodiment, the raw materials for preparation comprise, in parts by weight: 100 parts of water; 15-40 parts of soybean protein; 0.5-5 parts of alkali; 0.75-2.8 parts of silicate; 1.2-4.8 parts of a surfactant; 0.1-5 parts of polyamide polyamine epichlorohydrin resin; 0.01-3 parts of a compound shown in a structural formula (1).
In one embodiment, the base is an inorganic base or lewis base; the inorganic base is selected from any one or combination of several of sodium hydroxide, potassium hydroxide, calcium oxide or sodium borate; the Lewis base is triethylamine or calcium acetate; the silicate comprises sodium silicate and/or potassium silicate.
In one embodiment, the surfactant comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
In one embodiment, the compound of formula (1) is prepared from starting materials comprising an aminobenzo crown ether and a fluorophenyl isocyanate.
In one embodiment, the mass ratio of the polyamide polyamine epichlorohydrin resin to the compound represented by formula (1) is 2.5 to 4: 1.
in one embodiment, the raw material of the soybean protein biomass aldehyde-free glue further comprises acid for adjusting the pH value of the aldehyde-free glue, filler for improving the viscosity of the aldehyde-free glue, pyrethroid insecticide, bactericidal preservative sodium nitrite and potassium sorbate.
The invention also provides a method for preparing the soybean protein biomass formaldehyde-free glue, which specifically comprises the following steps:
(1) mixing alkali and water to prepare alkali liquor, adding silicate and surfactant into the alkali liquor, and stirring for 3-10min to obtain modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 60-120min to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound shown in a structural formula (1) into the soybean mixed solution obtained in the step (2), and stirring for 10-60min to obtain a soybean mixed solution;
(4) and (4) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-8, and uniformly stirring to obtain the soybean protein biomass formaldehyde-free glue.
In one embodiment, the preparation temperature is 50-75 ℃ when preparing the modified premix liquid in the step (1) and the soybean premix liquid in the step (2); when the soybean mixed solution in the step (3) is prepared, the preparation temperature is 30-60 ℃.
The invention also provides an application of the soybean protein biomass formaldehyde-free glue, and the soybean protein biomass formaldehyde-free glue can be used for wood artificial boards, various composite floors, bamboo floors and laminate floors; the wood-based panel is a blockboard, a bamboo plywood, a shaving board, a large shaving board, a fiberboard, a parallel lumber, an interlayer lumber and a laminated veneer lumber.
The soybean protein biomass formaldehyde-free adhesive is prepared from soybean protein, a formaldehyde-free crosslinking curing agent and the like, is a non-toxic environment-friendly adhesive, does not release formaldehyde or toxic organic matters in the production, transportation, application processes or finished product use processes, has high bonding strength and good water resistance, and completely reaches the use standard of the second type of adhesive.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of compounds prepared from raw materials containing dibenzo-18-crown-6 and pentafluorophenyl isocyanate, represented by structural formula (2).
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range of values bounded by upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1-5" is disclosed, the described range should be interpreted to include the ranges "1-4", "1-3", "1-2 and 4-5", "1-3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. The various embodiments, examples or illustrations described in this specification, as well as features of the various embodiments, examples or illustrations, may be combined and combined by those skilled in the art without contradiction.
In the description herein, reference to the description of the term "one preferred embodiment," "some preferred embodiments," "as a preferred aspect," "an example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the example or example is included in at least one example or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The invention aims to provide a soybean protein biomass formaldehyde-free glue, which at least comprises the following raw materials: water, soy protein, alkali, silicate, surfactant, polyamide polyamine epichlorohydrin resin and a compound shown in a structural formula (1);
wherein R is1、R2、R3、R4、R5Each independently may be hydrogen or fluorine, and R1、R2、R3、R4、R5Not both may be hydrogen.
The soybean protein biomass formaldehyde-free glue which is preferred in the invention comprises the following preparation raw materials in parts by weight: 100 parts of water; 15-40 parts of soybean protein; 0.5-5 parts of alkali; 0.75-2.8 parts of silicate; 1.2-4.8 parts of a surfactant; 0.1-5 parts of polyamide polyamine epichlorohydrin resin; 0.01-3 parts of a compound shown in a structural formula (1).
Soybean protein:
the soybean protein is a natural high molecular substance containing a complex 4-level structure, and the main components of the soybean protein are S7 and 115 globulin, which account for about 70 percent of the soybean protein. In soy protein isolate, the ratio of 2S, 7S, 11S and 15S is: 9.4%, 43%, 43.6% and 4.6%. The 7S globulin contains a main fragment of beta-conglobulin, which is a trimeric glycoprotein with the relative molecular weight of 15-20 ten thousand, and the 11S protein is a heterogeneous oligomeric protein with the relative molecular weight of 32-36 ten thousand. In terms of the smallest constitutional units, soy protein is composed of acidic amino acids (aspartic acid and glutamic acid) and corresponding amino compounds (asparagine and glutamine), nonpolar amino acids (alanine, valine, and leucine), basic amino acids (lysine and arginine), uncharged polar amino acids (glycine), and about 1% cystine. The 7S has high content of hydrophobic amino acid, the 11S has high content of sulfur-containing amino acid, and each protein molecule of the 11S globulin at least comprises 20 disulfide bonds and 2 sulfhydryl groups. Upon formation of the gel, the disulfide bond and sulfhydryl exchange reaction form an intermolecular disulfide bond. The two globulins have different compositions, structures and conformations, so that the functional characteristics of the soybean protein are different, thereby influencing the cementing property of the soybean protein glue. In a natural soybean globulin molecule, most polar and nonpolar groups in a polypeptide chain construct a stable multi-stage structure by van der waals force, hydrogen bonds, and hydrophobic interaction, and hydrophobic bonds are mutually bonded to the center of the protein molecule, and hydrophilic residues are arranged on the outer side of the protein molecule to form a hydrophilic region, thereby constituting a dense sphere with poor water resistance. Therefore, when the globulin is converted into the adhesive with excellent performance, structural connection bonds and interaction among multi-skin chains must be broken to fully expand protein molecules, and then an elastic macromolecular long-chain interwoven adhesive layer which is firmly adsorbed on a bonded phase interface can be formed. Such a three-dimensional network structure can disperse stress concentration and protect the adhesive layer. The fully expanded polypeptide chain is crosslinked at a higher temperature and a certain pressure, and various chemical crosslinks including disulfide bonds can be reformed to form a thermosetting and biodegradable adhesive layer.
The soy protein of the present invention is derived from soy, which may be used in the form of a soy defatted isolate, soy flour, soy meal, or roasted soy. Soy protein is typically obtained as soy flour (about 50 wt.% dry basis protein), and the soy flakes are ground to 100-200 mesh by a grinding process. The soy flour may be further purified, typically by solvent extraction of soluble carbohydrates, to yield a soy protein concentrate containing about 65 wt.% dry basis protein. The defatted soybeans may be further purified to produce Soy Protein Isolate (SPI) containing a protein content of at least about 85 wt.% dry basis.
As a preferred embodiment of the present invention, the soybean protein is Soybean Protein Isolate (SPI).
As a preferred embodiment of the present invention, the soybean protein is a processed soybean meal, and can be obtained by the following method: pulverizing soybean meal in a Chinese herbal medicine pulverizer for 5-10min, sieving with 100-plus-200 mesh sieve, and drying at 80 deg.C for 2 hr.
Although the protein of the soybean protein isolate is higher than that of the crushed bean pulp, in the formaldehyde-free glue system, the crushed bean pulp can also obtain a very good bonding effect, and the bean pulp has better economical and practical value compared with the soybean protein isolate.
The soybean protein biomass formaldehyde-free glue comprises, by weight, 100 parts of raw material water and 15-40 parts of soybean protein.
In one embodiment, the soy protein used in the present invention is 25-35 parts by weight.
Alkali, silicate, surfactant:
the base of the present invention is an inorganic base or a lewis base. The inorganic base is an oxide or hydroxide of group IA, or an oxide, hydroxide or borate of group IIA; preferably, the inorganic base is sodium hydroxide, potassium hydroxide, calcium oxide, or sodium borate. The lewis base is preferably triethylamine or calcium acetate. Under the treatment with preferably an alkali, carboxyl groups, phenolic hydroxyl groups and hydrophobe groups partially buried inside the protein are ionized, and the polypeptide chain is thereby dispersed. Preferably the base is sodium hydroxide.
The alkali content used in the invention is 0.5-5 parts by weight.
As a preferred embodiment of the present invention, the alkali content is 3 to 5%, and more preferably 4% by mass of the soybean protein.
The silicate according to the invention comprises sodium silicate and/or potassium silicate. The silicate can be matched with alkali to promote the development of the soybean protein and stabilize the crosslinking reaction in the glue making process.
The silicate used in the present invention is contained in an amount of 0.75 to 2.8 parts by weight.
In a preferred embodiment of the present invention, the silicate content is 5 to 7% by mass, and more preferably 6% by mass, of the soybean protein.
The surfactant according to the present invention includes an anionic surfactant and/or a cationic surfactant, and an anionic surfactant is more preferable. The anionic surfactant non-polar hydrocarbon chain may interact with the non-polar protein side chain groups and form a gel region, thereby enhancing the hydrophobicity of the non-aldehyde gel. Preferably a surfactant, is Sodium Dodecyl Sulfate (SDS) and/or Sodium Dodecyl Benzene Sulfonate (SDBS).
The content of the surfactant used in the invention is 1.2-4.8 parts by weight.
In a preferred embodiment of the present invention, the surfactant content is 2 to 12% by mass, and more preferably 8.5% by mass, of the soybean protein.
Polyamide polyamine epichlorohydrin resin:
the polyamide polyamine epichlorohydrin resin, PAE for short, is a water-soluble cationic thermosetting resin, has the characteristics of no formaldehyde, no toxicity, good wet strengthening effect and the like, and is widely applied to the papermaking industry. The PAE can effectively reduce the overall viscosity of the soy protein-based adhesive, so that the adhesive and the surface of the wood form a good wetting effect, namely, the adhesive is uniformly spread and filled into irregular textures and pores on the surface of the wood to form a continuous adhesive layer; and meanwhile, the PAE can form chemical bond reaction with carboxyl, hydroxyl and other groups on the surface of the wood, so that the bonding strength and the water resistance of the adhesive are improved.
The content of the polyamide polyamine epichlorohydrin resin used by the invention is 0.1 to 5 weight portions.
A compound represented by structural formula (1):
the structural formula of the compound represented by the structural formula (1) is as follows:
wherein R is1、R2、R3、R4、R5Each independently may be hydrogen or fluorine, and R1、R2、R3、R4、R5Not both may be hydrogen.
In one embodiment, the compound of formula (1) is prepared from starting materials comprising an aminobenzo crown ether and a fluorophenyl isocyanate.
The aminobenzene crown ether is dibenzo-18-crown-6.
Specific examples of the fluorine-containing phenyl isocyanate include 2, 4-difluorophenyl isocyanate, 3, 5-difluorophenyl isocyanate, 3, 4-difluorophenyl isocyanate, 2,3, 4-trifluorophenyl isocyanate, pentafluorophenyl isocyanate.
The specific preparation method of the compound shown in the structural formula (1) comprises the following steps:
placing 0.1mol of dibenzo-18-crown ether-6 into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dichloromethane, and stirring and uniformly mixing at 0 ℃ in an ice bath to obtain a solution a; putting 0.12mol of fluorine-containing phenyl isocyanate into a 250mL round-bottom flask with a stirring paddle, adding 15mL dichloromethane, and stirring and uniformly mixing at 0 ℃ in an ice bath to obtain a solution b; and (3) adding the solution a into the solution b at the temperature of 0 ℃ in an ice bath, stirring and mixing for 1-2h, returning to the room temperature, continuing stirring and mixing for 12-15h, and collecting the filtrate. Evaporating and concentrating the filtrate by using dichloromethane, and then recrystallizing by using hexane to obtain the compound shown in the structural formula (1).
As a preferred embodiment of the present invention, the compound represented by the structural formula (1) is prepared from a raw material comprising dibenzo-18-crown-6 and pentafluorophenyl isocyanate, and the resulting compound has a specific structural formula (2), as shown below:
the preparation method of the compound with the structural formula (2) comprises the following steps: placing 0.1mol of dibenzo-18-crown ether-6 into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dried dichloromethane, and stirring and mixing uniformly at 0 ℃ in an ice bath to obtain a solution a; putting 0.12mol of pentafluorophenyl isocyanate into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dried dichloromethane, and stirring and mixing uniformly at 0 ℃ in an ice bath to obtain a solution b; and adding the solution a into the solution b under an ice bath at 0 ℃, stirring and mixing for 1.5h, returning to room temperature, continuing stirring and mixing for 12h, and collecting the filtrate. Evaporating and concentrating the filtrate by using dichloromethane, and then recrystallizing by using hexane to obtain the compound shown in the structural formula (2). Using deuterated dichloromethane as a solvent, the chemical shift (ppm) of nuclear magnetic hydrogen spectrum is as follows: 7.43-7.56(m, H),6.66-6.81(m, H),5.63-5.75(s,1H),4.19-4.28(t,1H),3.59-3.65(t,2H), as shown in figure 1.
The content of the compound represented by the formula (1) used in the present invention is 0.01 to 3 parts by weight, and preferably 0.1 to 1 part by weight.
As a preferred embodiment of the present invention, the mass ratio of the polyamide polyamine epichlorohydrin resin to the compound represented by the formula (1) is 2.5 to 4: 1, more preferably 3: 1.
acids, fillers, and others:
as a preferred embodiment of the invention, the acid according to the invention is used to adjust the pH of the aldehyde-free glue to a value between 6 and 8. Preferably, the acid is phosphoric acid or oxalic acid, and can be matched with the addition of alkali to adjust the pH value during the preparation of the soybean gum, because in natural protein molecules, most polar and nonpolar groups have poor bonding effect due to the effects from Van der Waals force, hydrogen bonds, hydrophobic effect and the like, and when the pH value is hydrolyzed or increased, the protein molecules can be favorably dispersed and spread, and the polar and nonpolar groups are exposed and can be contacted with wood to interact, so that the bonding strength of the adhesive is improved; meanwhile, other raw material components without the aldehyde glue are matched in the pH value range, so that the required leakage group amount is more favorably reached.
The acid content used in the present invention is 0.1 to 5 parts by weight.
As a preferred embodiment of the present invention, the filler of the present invention is one or a mixture of two or more selected from the group consisting of flour, starch, tannin, diatomaceous earth, kaolin, bentonite, talc, montmorillonite, wheat flour, bark powder, nut shell powder, and corncob powder. The addition of the filler can improve the initial viscosity of the soybean gum and improve the prepressing effect on the board.
The filler content used in the present invention is 1 to 10 parts by weight.
As a preferred embodiment of the present invention, the aldehyde-free glue further comprises an insect repellent, such as a pyrethroid type insect repellent which is at least one of cypermethrin, fenvalerate, permethrin, bifenthrin and cyphenothrin.
As a preferred embodiment of the present invention, the aldehyde-free glue further comprises an industrial bactericide and a preservative, preferably sodium nitrite and potassium sorbate.
As a preferred embodiment of the present invention, swelling agents, viscosity modifiers and antifoaming agents commonly used in the art may also be added.
The content of the pyrethroid insecticide used in the invention is 0.001 to 1 part by weight; the content of the sodium nitrite used in the invention is 0.001-0.07 part; the content of the potassium sorbate used in the invention is 0.001 to 0.09 part.
The invention also provides a method for preparing the soybean protein biomass formaldehyde-free glue, which comprises the following steps:
(1) mixing alkali and water to prepare alkali liquor, adding silicate and surfactant into the alkali liquor, and stirring for 3-10min to obtain modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 60-120min to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound shown in a structural formula (1) into the soybean mixed solution obtained in the step (2), and stirring for 10-60min to obtain a soybean mixed solution;
(4) and (4) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-8, and uniformly stirring to obtain the soybean protein biomass formaldehyde-free glue.
As a preferred embodiment of the present invention, the method for preparing the soy protein biomass aldehyde-free glue specifically comprises the following steps:
(1) mixing alkali and water to prepare alkali liquor, adding silicate and surfactant into the alkali liquor, and stirring for 3-10min to obtain modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 60-120min to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound shown in a structural formula (1) into the soybean mixed solution obtained in the step (2), and stirring for 10-60min to obtain a soybean mixed solution;
(4) and (3) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-8 by using acid, stirring for 5-10min, adding a filler, an insect-resist agent and a sterilization preservative, and continuously stirring for 10-30min to obtain the soybean protein biomass formaldehyde-free glue.
As a preferred embodiment of the present invention, the temperature for preparing the modified premix in step (1) and the premix for soybean in step (2) is 50 to 75 ℃ and more preferably 58 to 65 ℃.
In a preferred embodiment of the present invention, the preparation temperature of the soybean mixture in the step (3) is 30 to 60 ℃, and more preferably 45 to 55 ℃.
The invention also provides an application of the soybean protein biomass formaldehyde-free glue, and the soybean protein biomass formaldehyde-free glue can be used for wood artificial boards, various composite floors, bamboo floors and laminate floors; the wood-based panel is a blockboard, a bamboo plywood, a shaving board, a large shaving board, a fiberboard, a parallel lumber, an interlayer lumber and a laminated veneer lumber.
The application method of the soybean protein biomass formaldehyde-free glue in the bonded wood comprises the following steps: coating the soybean protein biomass formaldehyde-free glue on the surface of a veneer of a wood artificial board by roller coating, scraper coating, curtain coating or spraying; then stacking a plurality of the veneers to form a sheet with a required thickness; and then the obtained sheet is aged, cold-pressed and hot-pressed to obtain the composite wood artificial board.
When the soybean protein biomass formaldehyde-free glue is prepared, firstly, alkali and silicate are adopted to treat soybean protein, the weak chemical bond breakage between the peptide bond of the main chain of the soybean protein and the molecular chain is synergistically promoted, the 1-level supermolecular structure of the soybean protein is destroyed, and the hydrophobic and nonpolar side chain groups buried in the protein are exposed along with the loosening of the molecular chain. The nonpolar hydrocarbon chain of the surfactant in the solution and the nonpolar protein side chain groups exposed inside the soybean protein further form a compound similar to micelles, so that the structure of protein molecules is further extended on the premise of avoiding excessive hydrolysis, contribution is made to the improvement of water-resistant cementing strength, and a homogeneous solution with low relative molecular mass and low viscosity is obtained.
The inventor unexpectedly discovers that the water resistance and the cementing strength of the soybean protein biomass formaldehyde-free glue can be remarkably improved by continuously adding the polyamide polyamine epichlorohydrin resin and the compound shown in the structural formula (1) into the solution obtained. The probable reason is presumed to be that the compound shown in the structural formula (1) promotes the crosslinking and curing effect of the polyamide polyamine epichlorohydrin resin on the aldehyde-free glue, and the ether oxygen bond, the fluorine and the amido bond in the compound shown in the structural formula (1) and the quaternary nitrogen heterocycle in the polyamide polyamine epichlorohydrin resin can form stronger combination with free amido, carboxyl and hydroxyl on the tail end and the side chain which are not combined in the soybean protein, and synergistically promote the formation of a crosslinking network. And the interaction between delocalized electrons exists between the fluorine-containing benzene rings, the interaction enhances the attraction between molecules, and the longer ether oxygen bond is easy to wind due to better flexibility, so that the stability of a cross-linked network is further improved. Therefore, the aldehyde-free glue forms a three-dimensional network framework which takes a small amount of uniformly distributed waterproof chemical bonds as a backbone core and has a compact structure on the surface of wood, effectively prevents water molecules from wedging to generate swelling to damage hydrogen bonds, ensures the bonding strength and stability of the aldehyde-free glue, and improves the water resistance. The present invention may also be explained without being limited to this mechanism.
As preferred embodiments of the present invention:
embodiment 1, a soy protein biomass aldehyde-free gum comprising the following raw materials: water, soy protein, alkali, silicate, surfactant, polyamide polyamine epichlorohydrin resin and a compound shown in a structural formula (1);
wherein R is1、R2、R3、R4、R5Each independently may be hydrogen or fluorine, and R1、R2、R3、R4、R5Not both may be hydrogen.
Embodiment 2, a soy protein biomass formaldehyde-free glue, which comprises the following preparation raw materials in parts by weight: 100 parts of water; 15-40 parts of soybean protein; 0.5-5 parts of alkali; 0.75-2.8 parts of silicate; 1.2-4.8 parts of a surfactant; 0.1-5 parts of polyamide polyamine epichlorohydrin resin; 0.01-3 parts of a compound shown in a structural formula (1).
Embodiment 3, the difference from embodiment 1 is that the base is an inorganic base or a lewis base; the inorganic base is selected from any one or combination of several of sodium hydroxide, potassium hydroxide, calcium oxide or sodium borate; the Lewis base is triethylamine or calcium acetate; the silicate comprises sodium silicate and/or potassium silicate.
Embodiment 4 differs from embodiment 1 in that the surfactant comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
Embodiment 5 differs from embodiment 1 in that the compound represented by the structural formula (1) is prepared from a raw material comprising aminobenzene crown ether and fluorine-containing phenyl isocyanate.
Embodiment 6 differs from embodiment 1 in that the mass ratio of the polyamide polyamine epichlorohydrin resin to the compound represented by the formula (1) is 2.5 to 4: 1.
embodiment 7 is different from embodiment 1 in that the raw material of the soy protein biomass aldehyde-free glue further comprises an acid for adjusting the pH of the aldehyde-free glue, a filler for improving the viscosity of the aldehyde-free glue, a pyrethroid insecticide, a bactericidal preservative sodium nitrite and potassium sorbate.
Embodiment 8, a method of making the soy protein biomass aldehyde-free gum of embodiments 1-7, comprising the steps of:
(1) mixing alkali and water to prepare alkali liquor, adding silicate and surfactant into the alkali liquor, and stirring for 3-10min to obtain modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 60-120min to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound shown in a structural formula (1) into the soybean mixed solution obtained in the step (2), and stirring for 10-60min to obtain a soybean mixed solution;
(4) and (4) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-8, and uniformly stirring to obtain the soybean protein biomass formaldehyde-free glue.
Embodiment 9 differs from embodiment 8 in that the preparation temperature is 50 to 75 ℃ when preparing the modified premix of step (1) and the soybean premix of step (2); when the soybean mixed solution in the step (3) is prepared, the preparation temperature is 30-60 ℃.
Embodiment 10, use of the soy protein biomass aldehyde-free glue of any one of embodiments 1-7 above for wood-based panels and various composite, bamboo, and laminated flooring boards; the wood-based panel is a blockboard, a bamboo plywood, a shaving board, a large shaving board, a fiberboard, a parallel lumber, an interlayer lumber and a laminated veneer lumber.
The present invention is described in more detail below by way of specific examples and comparative examples, but it is to be understood that these examples are illustrative only and not limiting, and that the starting materials used in the following examples and comparative examples are commercially available without specific indication.
Wherein,
soy protein a 1: soy protein isolate, food grade SPI (protein content 93.4%), available from harbin gaku soy food llc.
Soy protein a 2: the soybean meal powder is obtained by crushing low-temperature soybean meal in a Chinese herbal medicine crusher for 10min, sieving the crushed soybean meal with a 200-mesh sieve, and drying the sieved soybean meal at 80 ℃ for 2 h. The low-temperature soybean meal (the main components of which are 6.44% of water, 5.88% of ash, 46% of crude protein, 1.6% of grease and 35.6% of carbohydrate) is purchased from grain and oil industry ltd of hong Kong and Zhenghai of Jiangsu province.
Compound B1: a compound prepared from starting materials comprising dibenzo-18-crown-6 and 3, 5-difluorophenyl isocyanate, the preparation method comprising: placing 0.1mol of dibenzo-18-crown ether-6 into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dichloromethane, and stirring and uniformly mixing at 0 ℃ in an ice bath to obtain a solution a; placing 0.12mol of 3, 5-difluorophenyl isocyanate into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dichloromethane, and uniformly stirring and mixing at 0 ℃ in an ice bath to obtain a solution b; and adding the solution a into the solution b under an ice bath at 0 ℃, stirring and mixing for 1h, returning to room temperature, continuing stirring and mixing for 15h, and collecting the filtrate. The filtrate was concentrated by evaporation with dichloromethane and recrystallized from hexane to give compound B1.
Compound B2: a compound prepared from starting materials comprising dibenzo-18-crown-6 and pentafluorophenyl isocyanate, the method of preparation: placing 0.1mol of dibenzo-18-crown ether-6 into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dichloromethane, and stirring and uniformly mixing at 0 ℃ in an ice bath to obtain a solution a; placing 0.12mol of 3, 5-difluorophenyl isocyanate into a 250mL round-bottom flask with a stirring paddle, adding 15mL of dichloromethane, and uniformly stirring and mixing at 0 ℃ in an ice bath to obtain a solution b; and adding the solution a into the solution b under an ice bath at 0 ℃, stirring and mixing for 2 hours, returning to the room temperature, continuing stirring and mixing for 12 hours, and collecting the filtrate. The filtrate was concentrated by evaporation with dichloromethane and recrystallized from hexane to obtain compound B2, which is the compound represented by the aforementioned structural formula (2).
Example 1: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 225 parts of soybean protein A; 1 part of sodium hydroxide; 1.5 parts of sodium silicate; 2.1 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 20.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 2: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 10.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 3: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 20.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 4: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.15 part of polyamide polyamine epichlorohydrin resin; 20.45 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 5: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.35 part of polyamide polyamine epichlorohydrin resin; 20.35 parts of a compound B; 1.2 parts of starch; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 6: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 235 parts of soybean protein A; 1.4 parts of sodium hydroxide; 2.1 parts of sodium silicate; 2.9 parts of sodium dodecyl sulfate; 2.1 parts of polyamide polyamine epichlorohydrin resin; 20.7 parts of a compound B; 1.3 parts of starch; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 7: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 235 parts of soybean protein A; 1.4 parts of sodium hydroxide; 2.1 parts of sodium silicate; 2.9 parts of sodium dodecyl sulfate; 2.1 parts of polyamide polyamine epichlorohydrin resin; 20.3 parts of a compound B; 1.3 parts of starch; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 8: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 115 parts of soybean protein A; 0.6 part of sodium hydroxide; 0.9 part of sodium silicate; 1.3 parts of sodium dodecyl sulfate; 0.45 part of polyamide polyamine epichlorohydrin resin; 20.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Example 9: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 130 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 20.15 parts of a compound B; 1.2 parts of starch; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 1: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 2: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 130 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 0.45 part of polyamide polyamine epichlorohydrin resin; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 3: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 2.5 parts of sodium dodecyl benzene sulfonate; 20.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 4: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 0.45 part of polyamide polyamine epichlorohydrin resin; 20.15 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 5: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 20.35 parts of a compound B; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
Comparative example 6: the preparation raw materials comprise the following components in parts by weight: 100 parts of water; 230 parts of soybean protein A; 1.2 parts of sodium hydroxide; 1.8 parts of sodium silicate; 0.45 part of polyamide polyamine epichlorohydrin resin; 1.2 parts of kaolin; 0.1 part of cypermethrin; 0.1 part of sodium nitrite; and 0.01 part of potassium sorbate.
The preparation methods of examples 1 to 9 and comparative examples 1 to 6 were:
(1) mixing sodium hydroxide and water to prepare an alkali liquor, adding sodium silicate and a surfactant sodium dodecyl sulfate or sodium dodecyl benzene sulfonate into the alkali liquor, and stirring for 10min at 60 ℃ to obtain a modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 80min at 60 ℃ to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound B1 or B2 into the soybean mixed solution obtained in the step (2), and stirring for 30min at 50 ℃ to obtain a soybean mixed solution;
wherein, the polyamide polyamine epichlorohydrin resin is added into the mixture by using an aqueous solution with the mass concentration of 12.5 percent; adding the compound B1 or B2 in an aqueous solution with the mass concentration of 30%;
(4) and (3) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-7 by using oxalic acid with the mass concentration of 40%, stirring for 10min, sequentially adding filler kaolin or starch, cypermethrin serving as an insect-resist agent, sodium nitrite and potassium sorbate serving as a sterilization preservative, and continuously stirring for 10min to obtain the soybean protein biomass formaldehyde-free glue.
The water loss performance test of the soybean protein biomass formaldehyde-free glue prepared in the examples 1 to 9 and the comparative examples 1 to 6 is mainly used for representing the water resistance of the formaldehyde-free glue after curing, and the specific index is the content of extraction residues.
The specific method comprises the following steps:
firstly, drying the soybean protein biomass formaldehyde-free glue in a constant-temperature drying oven at 120 ℃ until the soybean protein biomass formaldehyde-free glue is completely dried, and putting the dried soybean protein biomass formaldehyde-free glue into a dryer to cool the dried soybean protein biomass formaldehyde-free glue to room temperature. Then grinding and sieving are carried out, and the mass of the sample is weighed to be 5g +/-0.1 g, and the accuracy is 0.001 g. And (3) carrying out Soxhlet water extraction on the sample for 24h, finally drying the sample in a constant-temperature drying box at 120 ℃ to constant weight, cooling the dried sample in a dryer for 30min, taking out the dried sample, and immediately weighing the sample to the accuracy of 0.001 g. The extraction residue content was calculated as follows: extraction residue% (mass of no aldehyde glue after extraction/mass of no aldehyde glue before extraction) × 100%; the results are measured in parallel for three times, and the difference of the results is not more than 0.5 percent; the arithmetic mean of the three valid measurements was taken to the nearest 0.1%. The test results are detailed in table 1.
The soy protein biomass non-aldehyde glue obtained from examples 1-9 and comparative examples 1-6 was used to press plywood: the eucalyptus veneer is subjected to glue application, aging, cold pressing, hot pressing and cutting processes to prepare the eucalyptus plywood, wherein the glue application amount is 350g/m2(ii) a Aging for 35 min; coldThe pressure is 1.0MPa, and the cold pressing time is 30 min; the hot pressing temperature is 120 ℃, the hot pressing pressure is 1.0MPa, and the hot pressing time is 1min/mm of plate thickness.
The plywood obtained was subjected to the following evaluation tests:
according to the standard of GB/T17657-1999 "test method for physical and chemical properties of artificial boards and decorative artificial boards", MT-5504 type universal mechanical testing machine is adopted to measure dry-state bonding strength and wet-state bonding strength. Wherein the wet-state bonding strength is that the test piece is immersed in hot water at the temperature of 63 +/-3 ℃ for 3 hours, taken out and cooled for 10 minutes, and then the bonding strength of the test piece is tested. The dry state cementation strength is obtained by directly performing a dry state test on a test piece with the water content meeting the requirement. The test results are detailed in table 1.
TABLE 1
As can be seen from the detection data in Table 1, after the soybean protein biomass formaldehyde-free glue obtained by the invention is subjected to hot water extraction, the remainder is a water-insoluble substance, and the higher the content is, the more stable the formed reticular cross-linked structure is, so that the water resistance is obviously improved. The dry state cementation strength is more than 2.1MPa, the wet state treatment does not cause glue splitting, the phenomena of interface stripping, cracking and the like do not exist between the adhesives, the wet state cementation strength reaches more than 1.4MPa, and the use standard of the two types of glue is completely reached. The soybean protein biomass formaldehyde-free adhesive is prepared from soybean protein, a formaldehyde-free crosslinking curing agent, a filler and the like, is a non-toxic environment-friendly adhesive, and does not release formaldehyde or toxic organic matters in the production, transportation, application processes or finished product use.
The foregoing examples are illustrative only, and serve to explain some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.
Claims (10)
1. The soybean protein biomass formaldehyde-free glue is characterized by at least comprising the following raw materials: water, soy protein, alkali, silicate, surfactant, polyamide polyamine epichlorohydrin resin and a compound shown in a structural formula (1);
wherein R is1、R2、R3、R4、R5Can be respectively and independently arrangedIs hydrogen or fluorine, and R1、R2、R3、R4、R5Not both may be hydrogen.
2. The soy protein biomass aldehyde-free glue of claim 1, wherein the raw materials for the preparation comprise, in parts by weight: 100 parts of water; 15-40 parts of soybean protein; 0.5-5 parts of alkali; 0.75-2.8 parts of silicate; 1.2-4.8 parts of a surfactant; 0.1-5 parts of polyamide polyamine epichlorohydrin resin; 0.01-3 parts of a compound shown in a structural formula (1).
3. The soy protein biomass aldehyde-free glue of claim 1, wherein the base is an inorganic base or a lewis base; the inorganic base is selected from any one or combination of several of sodium hydroxide, potassium hydroxide, calcium oxide or sodium borate; the Lewis base is triethylamine or calcium acetate; the silicate comprises sodium silicate and/or potassium silicate.
4. The soy protein biomass aldehyde-free glue of claim 1, wherein the surfactant comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
5. The soy protein biomass aldehyde-free glue of claim 1, wherein the compound of formula (1) is prepared from a starting material comprising an aminobenzo crown ether and a fluorophenyl isocyanate.
6. The soy protein biomass aldehyde-free glue of claim 1, wherein the mass ratio of the polyamide polyamine epichlorohydrin resin to the compound represented by formula (1) is 2.5-4: 1.
7. the soy protein biomass aldehyde-free glue of claim 1, wherein the raw materials of the soy protein biomass aldehyde-free glue further comprise an acid for adjusting the pH value of the aldehyde-free glue, a filler for improving the viscosity of the aldehyde-free glue, a pyrethroid insecticide, a bactericidal preservative sodium nitrite and potassium sorbate.
8. A method for preparing the soy protein biomass aldehyde-free glue of any one of claims 1-6, comprising the steps of:
(1) mixing alkali and water to prepare alkali liquor, adding silicate and surfactant into the alkali liquor, and stirring for 3-10min to obtain modified premixed solution;
(2) adding soybean protein into the modified premix obtained in the step (1), and stirring and mixing for 60-120min to obtain a soybean premix;
(3) adding polyamide polyamine epoxy chloropropane resin and a compound shown in a structural formula (1) into the soybean mixed solution obtained in the step (2), and stirring for 10-60min to obtain a soybean mixed solution;
(4) and (4) adjusting the pH value of the soybean mixed solution obtained in the step (3) to 6-8, and uniformly stirring to obtain the soybean protein biomass formaldehyde-free glue.
9. The method according to claim 8, wherein the modified premix in the step (1) and the soybean premix in the step (2) are prepared at a temperature of 50 to 75 ℃; when the soybean mixed solution in the step (3) is prepared, the preparation temperature is 30-60 ℃.
10. Use of the soy protein biomass formaldehyde-free gum as claimed in any one of claims 1 to 7, wherein: the soybean protein biomass formaldehyde-free glue can be used for wood artificial boards, various composite floors, bamboo floors and laminate floors; the wood-based panel is a blockboard, a bamboo plywood, a shaving board, a large shaving board, a fiberboard, a parallel lumber, an interlayer lumber and a laminated veneer lumber.
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