CN111892887B - Metal ion crosslinked protein adhesive and preparation method thereof - Google Patents

Metal ion crosslinked protein adhesive and preparation method thereof Download PDF

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Publication number
CN111892887B
CN111892887B CN202010805273.9A CN202010805273A CN111892887B CN 111892887 B CN111892887 B CN 111892887B CN 202010805273 A CN202010805273 A CN 202010805273A CN 111892887 B CN111892887 B CN 111892887B
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collagen
metal ion
hydrophobic monomer
protein adhesive
mass
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CN111892887A (en
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郝晓丽
邓志峰
丁镠
包维维
朱佳新
童婷
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Shaanxi University of Technology
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Shaanxi University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • 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

Abstract

The invention discloses a preparation method of a metal ion crosslinking type protein adhesive, which comprises the following steps: preparing a certain amount of collagen into a collagen aqueous solution with the mass concentration of 10-50%, hydrolyzing, adding a hydrophobic monomer, an initiator and an anionic emulsifier into the collagen aqueous solution according to the proportion of 20-100%, 0.5-2.5% and 0.1-0.5% of the mass of the collagen, and reacting for 2-4 hours at 35-75 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system; and slowly dripping a polyvalent metal compound into the obtained hydrophobic monomer grafted collagen emulsion system under the action of magnetic stirring, and aging for 1-3 h to obtain the metal ion crosslinked protein adhesive. According to the invention, the biomass resource collagen is used as the raw material of the adhesive, and water is used as the medium, so that the cost is reduced, and the problem of environmental pollution is relieved.

Description

Metal ion crosslinked protein adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of aldehyde-free adhesives, and particularly relates to a metal ion crosslinking type protein adhesive and a preparation method thereof.
Background
The adhesive industry, especially the wood industry, has been the era of synthetic petroleum-based adhesives based on "trioxane adhesives". The urea-formaldehyde resin, the phenolic resin and the melamine-formaldehyde resin adhesive have the advantages of high bonding strength, low price, simple manufacturing process, convenient use and the like, so the 'formaldehyde-formaldehyde adhesive' still occupies a large share in the wood and artificial board markets in China. However, the formaldehyde-formaldehyde adhesives release free formaldehyde in the production, storage and use processes, most adhesives are solvent-based products, volatile organic compounds such as benzene and toluene are used as solvents, and the organic solvents can be directly volatilized into the atmosphere in the use process to pollute the environment and harm the health of human bodies. The use of volatile organic compounds is restricted by the enactment of regulations by many government agencies both at home and abroad. Meanwhile, the production of the adhesives depends on non-renewable petroleum resources, and with the appearance of worldwide energy crisis and the increasingly prominent problem of environmental pollution, the development of green bio-based, solvent-free and aldehyde-free adhesives, the search of new production raw materials and the development of new production process technologies become necessary trends of the development of the adhesive industry.
The animal protein is a renewable biomass polymer material, and the molecular chain of the animal protein contains rich active groups such as amino groups, carboxyl groups and the like, and has certain reactivity, adhesiveness and film-forming property. However, pure collagen has certain water absorption, and the water resistance and the adhesion of the collagen are further improved by means of opening protein molecular chains, introducing hydrophobic chains, adding metal ions, performing coordination and complexation with active groups such as amino groups and carboxyl groups on the protein molecular chains to form a cross-linked network structure and the like. Because the protein latex is heated and water is volatilized in the process of curing to form a film or pressing a plywood, latex particles are changed into a close packing state due to the separation state of the latex particles, and the fusion film is cured. During the period, active functional groups such as amino, carboxyl and the like with chelation on the molecular chain of the protein latex firstly form ionic complexation with metal ions, and then the ionic complexation rearrangement is caused by kinetic factors to form a more thermodynamically stable coordination complex. The cross-linking method can increase the relative molecular mass of the original linear macromolecule by times, and the mechanical strength, water resistance, weather resistance, bonding strength and the like of the protein latex coating can be obviously improved.
Disclosure of Invention
The invention aims to provide a metal ion crosslinking type protein adhesive and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a metal ion crosslinking type protein adhesive comprises the following steps:
s1, preparing a certain amount of collagen into a collagen water solution with the mass concentration of 10-50%, hydrolyzing the collagen, opening molecular chains of the collagen, and releasing free active radicals;
s2, taking the collagen hydrolysate obtained in the step S1 as a water phase, adding a hydrophobic monomer, an initiator and an anionic emulsifier into the collagen aqueous solution according to the proportion of 20-100%, 0.5-2.5% and 0.1-0.5% of the mass of the collagen, and reacting for 2-4 hours at 35-75 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system;
s3, slowly dripping a polyvalent metal compound into the obtained hydrophobic monomer grafted collagen emulsion system under the action of magnetic stirring, and aging for 1-3 h to obtain the metal ion crosslinked protein adhesive.
Further, in step S1, the collagen molecular chains are opened by the method of trypsin hydrolysis.
Further, in step S2, the hydrophobic monomer is one of acrylate monomers such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like; the initiator is one of a redox initiation system or a water-soluble single-component initiator.
Further, in step S2, a hydrophobic monomer, an initiator, and an anionic emulsifier are added to a collagen aqueous solution with a mass concentration of 30% by mass based on 50%, 1.5%, and 0.3% of the collagen, respectively, and reacted at 55 ℃ for 3 hours to obtain a hydrophobic monomer-grafted collagen emulsion system.
Further, in step S3, a polyvalent metal compound is slowly added dropwise to the obtained hydrophobic monomer-grafted collagen emulsion system in an amount of 10% to 30% by mass of the graft polymer, and in order to prevent the polyvalent metal ions from deteriorating the stability of the emulsion obtained in step S2, the polyvalent metal ion compound used is mainly one of metal oxides, hydroxides, weak acid salts of beryllium, cadmium, calcium, magnesium, zinc, barium, strontium, aluminum, bismuth, tin, lead, cobalt, nickel, and the like, or ammonia or amine complexes thereof.
Further, in step S3, when the polyvalent metal ion compound is a metal oxide, hydroxide or weak acid salt of beryllium, cadmium, calcium, magnesium, zinc, barium, strontium, aluminum, bismuth, tin, lead, cobalt, nickel, NH in an amount of 3% to 30% of the amount of the metal ion compound is added to the system4OH。
Further, in step S3, under the action of magnetic stirring, slowly dropping a polyvalent metal compound into the emulsion of step S2 according to the proportion of 20% of the mass of the grafted polymer, and aging for 2h to obtain the metal ion crosslinked protein adhesive.
The invention also provides a metal ion crosslinking protein adhesive, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the collagen adopted by the method is a renewable natural polymer material completely separated from petroleum resources, is widely present in parts of hoof tissues, skin, bones and the like of animals, has rich sources and low preparation cost; the molecular chain of the collagen has rich chelate active groups such as carboxyl, amino, hydroxyl and the like, and the collagen is easy to coordinate and complex with polyvalent metal ions so as to improve the defect of poor water resistance of the collagen, endow the collagen with better adhesive property, reduce the cost, improve the water resistance and the adhesive property, release no formaldehyde in the production and use processes and have certain environmental protection superiority; in addition, the preparation method provided by the invention can be used for production only by common conventional chemical equipment, is simple and feasible, and the obtained ionic crosslinking type protein emulsion adhesive has good storage stability, does not harm human health and environment in the production and use processes, and has good industrial feasibility and application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
Fig. 1 is a process flow diagram of a preparation method of a metal ion crosslinked protein adhesive according to an embodiment of the present invention.
Fig. 2 is a photograph showing the static water contact angle of the adhesive films obtained in examples 1, 2 and 3 of the present invention.
FIG. 3 is a schematic view of a three-ply panel lap joint in an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in fig. 1, a preparation method of a metal ion crosslinked protein adhesive comprises the following steps:
s1, accurately weighing 30g of collagen, preparing into a collagen water solution with the mass concentration of 10%, and performing trypsin hydrolysis treatment to release more free active groups on a molecular chain; wherein, the hydrolysis conditions are as follows: heating to 45 deg.C, adding trypsin powder 0.2% of gelatin, performing enzymolysis for 10min, rapidly heating to 90 deg.C, maintaining for 5min to inactivate trypsin, rapidly cooling to normal temperature, and filtering with gauze;
s2, taking the 10% hydrolyzed collagen solution obtained in S1 as a water phase, and respectively adding hydrophobic monomer butyl acrylate and potassium persulfate-ferrous sulfate (K) of an oxidation-reduction initiation system into the collagen water solution according to the proportion of 20%, 0.5% and 0.1% of the mass of the collagen2S2O4-FeSO4) And the anionic emulsifier sodium laurate (C)11H23COONa) Reacting for 2 hours at 35 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system; wherein, the oxidant K2S2O4And a reducing agent FeSO4The mass ratio of the components is 10:1,
s3, under the action of magnetic stirring, adding basic aluminum acetate [ (CH) according to the proportion of 10 percent of the mass of the grafted polymer3COO）2(OH)Al]Slowly dripping the hydrophobic monomer grafted collagen emulsion system, and aging for 1h to obtain the metal ion crosslinked protein adhesive. Testing the hydrophobic property of the protein adhesive film prepared by the invention by using a static water contact angle tester; the three-layer poplar plywood is pressed by the protein adhesive prepared by the invention, the bonding strength is determined by referring to the method of national standard GB/T33334-.
Example 2
A preparation method of a metal ion crosslinking type protein adhesive comprises the following steps:
s1, accurately weighing 30g of collagen, preparing into a collagen water solution with the mass concentration of 30%, and performing trypsin hydrolysis operation to release more free active groups on molecular chains, wherein the hydrolysis conditions are as follows: heating to 45 deg.C, adding trypsin powder 0.2% of gelatin, performing enzymolysis for 20min, rapidly heating to 90 deg.C, maintaining for 5min to inactivate trypsin, rapidly cooling to normal temperature, and filtering with gauze.
S2, taking the 30% hydrolyzed collagen solution obtained in S1 as a water phase, and respectively adding hydrophobic monomer ethyl acrylate and initiator potassium persulfate K into the collagen water solution according to the proportion of 50%, 1.5% and 0.3% of the collagen mass2S2O4And the anionic emulsifier sodium palmitate (C)15H31COONa) and reacting for 3 hours at the temperature of 55 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system;
s3, under the action of magnetic stirring, zinc tetra-ammino [ Zn (NH) ] hydroxide in an amount of 20% of the mass of the graft polymer3)4](OH)]Slowly dripping the hydrophobic monomer grafted collagen emulsion system, and aging for 2h to obtain the metal ion crosslinked protein adhesive. Testing the hydrophobic property of the protein adhesive film prepared by the invention by using a static water contact angle tester; use the present inventionThe three-layer poplar plywood is pressed by the prepared protein adhesive, and the bonding strength is determined by referring to a method of national standard GB/T33334-: folding and gluing the main surface parts of the two base materials together to form a single lap joint, and under the action of a tensile load parallel to the axial direction of a lap joint surface, damaging the single lap joint, and measuring the peak value of the maximum shear stress borne by the lap joint. And (4) calculating the average of the obtained numerical values, and calculating the strength of the adhesive according to P = F/S. Wherein: p is adhesive shear strength (MPa); f is the maximum force (N) required to press open the sample; s is the bonding area (m)2). The sample was prepared according to the triple-ply lap joint schematic shown in fig. 3, the specifications of the sample being: 50 mm. times.50 mm. times.2 mm, the coated area was 2X 20 mm. times.40 mm, and the amount of coating was 1 mm. Setting the temperature at 50 ℃, hot-pressing for a certain time, standing at room temperature for 6 hours, taking out, and testing the maximum shear stress by using a universal tensile machine. The maximum peak shear stress of the test specimen was measured by a universal tensile machine under the conditions of an experimental force of 20KN, a tensile speed of 30mm/min and a tensile force of 1KN/s, and the results are shown in Table 1.
Example 3
A preparation method of a metal ion crosslinking type protein adhesive comprises the following steps:
s1, accurately weighing 30g of collagen, preparing into a collagen water solution with the mass concentration of 50%, and performing trypsin hydrolysis so as to release more free active groups on molecular chains. The hydrolysis conditions were as follows: heating to 45 deg.C, adding trypsin powder 0.2% of gelatin, performing enzymolysis for 30min, rapidly heating to 90 deg.C, maintaining for 5min to inactivate trypsin, rapidly cooling to normal temperature, and filtering with gauze.
S2, taking the 50% hydrolyzed collagen solution obtained in S1 as a water phase, and respectively adding a hydrophobic monomer methyl methacrylate and an initiator ammonium persulfate [ (NH) into the water phase according to the proportion of 100%, 2.5% and 0.5% of the mass of the collagen4）2S2O8]And the anionic emulsifier sodium lauryl sulfate (C)12H25SO4Na) and reacting for 4 hours at the temperature of 75 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system;
s3, under the action of magnetic stirring, adding calcium acetate according to the proportion of 30 percent of the mass of the graft polymer
[(CH3COO)2Ca]Slowly adding into the emulsion of the step 2) in a dropwise manner, and simultaneously adding NH with the dosage of 30 percent of calcium acetate4And OH, aging for 3h to obtain the metal ion crosslinking protein adhesive. Testing the hydrophobic property of the protein adhesive film prepared by the invention by using a static water contact angle tester; the three-layer poplar plywood is pressed by the protein adhesive prepared by the invention, the bonding strength is determined by referring to the method of national standard GB/T33334-.
TABLE 1
Sample (I) Bonding strength (dry state)/MPa
Example 1 0.89
Example 2 0.94
Example 3 1.18
The metal ion crosslinked protein adhesive takes biomass resources as raw materials and water as a medium, has the unique advantage of zero formaldehyde release in the using process of the product, and is environment-friendly; the obtained adhesive emulsion has good storage stability, and the adhesive film has good water resistance, and the bonding strength is close to or even better than that of phenolic glue, urea-formaldehyde glue and melamine-formaldehyde glue. The production can be carried out only by common conventional chemical equipment, the requirement on production equipment is low, the production process is simple and feasible, and the large-scale and industrial production is facilitated.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A preparation method of a metal ion crosslinking type protein adhesive is characterized by comprising the following steps:
s1, preparing a certain amount of collagen into a collagen water solution with the mass concentration of 10-50%, hydrolyzing the collagen, opening molecular chains of the collagen, and releasing free active radicals;
s2, taking the collagen hydrolysate obtained in the step S1 as a water phase, adding a hydrophobic monomer, an initiator and an anionic emulsifier into the collagen aqueous solution according to the proportion of 20-100%, 0.5-2.5% and 0.1-0.5% of the mass of the collagen, and reacting for 2-4 hours at 35-75 ℃ to obtain a hydrophobic monomer grafted collagen emulsion system;
s3, slowly dripping a polyvalent metal compound into the obtained hydrophobic monomer grafted collagen emulsion system under the action of magnetic stirring, and aging for 1-3 h to obtain the metal ion crosslinked protein adhesive.
2. The method of claim 1, wherein in step S1, the collagen molecular chains are opened by trypsin hydrolysis.
3. The method for preparing the metal ion crosslinked protein adhesive according to claim 1, wherein in step S2, the hydrophobic monomer is an acrylate monomer; the initiator is one of a redox initiation system or a water-soluble single-component initiator.
4. The method of claim 1, wherein in step S2, the hydrophobic monomer, the initiator and the anionic emulsifier are added to a collagen aqueous solution with a mass concentration of 30% by mass at 50%, 1.5% and 0.3% of the collagen mass, respectively, and reacted at 55 ℃ for 3 hours to obtain a hydrophobic monomer grafted collagen emulsion system.
5. The method according to claim 1, wherein in step S3, a polyvalent metal compound is slowly added dropwise to the obtained hydrophobic monomer grafted collagen emulsion system in an amount of 10-30% by weight of the grafted polymer, and the polyvalent metal compound is one of metal oxides, hydroxides, salts of weak acids, or ammonia or amine complexes thereof of beryllium, cadmium, calcium, magnesium, zinc, barium, strontium, aluminum, bismuth, tin, lead, cobalt, and nickel.
6. The method according to claim 5, wherein in step S3, when the multivalent metal ion compound is a metal oxide, hydroxide or weak acid salt of beryllium, cadmium, calcium, magnesium, zinc, barium, strontium, aluminum, bismuth, tin, lead, cobalt, nickel, NH is added to the system in an amount of 3% -30% of the amount of the metal ion compound4OH。
7. The method for preparing the metal ion crosslinked protein adhesive according to claim 1, wherein in step S3, under the action of magnetic stirring, the polyvalent metal compound is slowly added dropwise into the emulsion of step S2 according to a ratio of 20% of the mass of the graft polymer, and aging is carried out for 2h, so as to obtain the metal ion crosslinked protein adhesive.
8. A metal ion crosslinked protein adhesive prepared by the preparation method according to any one of claims 1 to 7.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103669109A (en) * 2013-12-13 2014-03-26 陕西科技大学 Preparation method for paper-making sizing agent
CN104628970A (en) * 2014-12-02 2015-05-20 陕西科技大学 Method for preparing scrap leather industrial gelatine hydrolyzed collagen based papermaking sizing agent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090129423A (en) * 2007-03-09 2009-12-16 바텔리 메모리얼 인스티튜트 Protein stabilized latex polymer emulsions, method of making, and adhesives containing such emulsions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103669109A (en) * 2013-12-13 2014-03-26 陕西科技大学 Preparation method for paper-making sizing agent
CN104628970A (en) * 2014-12-02 2015-05-20 陕西科技大学 Method for preparing scrap leather industrial gelatine hydrolyzed collagen based papermaking sizing agent

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