CN110835518A - Formaldehyde-free soybean protein powder adhesive and preparation method and application thereof - Google Patents

Formaldehyde-free soybean protein powder adhesive and preparation method and application thereof Download PDF

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Publication number
CN110835518A
CN110835518A CN201911178881.5A CN201911178881A CN110835518A CN 110835518 A CN110835518 A CN 110835518A CN 201911178881 A CN201911178881 A CN 201911178881A CN 110835518 A CN110835518 A CN 110835518A
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adhesive
free
powder
aldehyde
lignin
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范东斌
储富祥
李改云
陈媛
张冉
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Research Institute of Wood Industry of Chinese Academy of Forestry
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Research Institute of Wood Industry of Chinese Academy of Forestry
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J189/00Adhesives based on proteins; Adhesives based on derivatives thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00Pretreatment of moulding material
    • B27N1/02Mixing the material with binding agent
    • B27N1/0209Methods, e.g. characterised by the composition of the agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • C08K2003/162Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

Abstract

The invention discloses an aldehyde-free soy protein powder adhesive and a preparation method and application thereof, and particularly relates to the field of adhesives, wherein the aldehyde-free soy protein powder adhesive comprises the following main materials in parts by weight: 35-45 parts of vegetable protein, 2-10 parts of lignin epoxidation modified substance powder and 0.6-1.5 parts of an activating agent, and the balance of auxiliary materials, wherein the auxiliary materials comprise a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is 5-10: 1. according to the invention, the vegetable protein and lignin epoxidation modified substance powder is adopted as the main raw material, the raw material belongs to renewable resources, the requirement range on protein content is large, the raw material source is wide, the raw material does not contain benzene and formaldehyde substances, the prepared vegetable protein adhesive does not have the problem of formaldehyde release when used for manufacturing artificial boards, and the adhesive is simple to operate and convenient to prepare and use when used.

Description

Formaldehyde-free soybean protein powder adhesive and preparation method and application thereof
Technical Field
The invention relates to the field of adhesives, in particular to an aldehyde-free soybean protein powder adhesive and a preparation method and application thereof.
Background
Along with the reduction of forest resources and the shortage of wood, the artificial board becomes an important material for human production and life, the artificial board industry is also developed dramatically, the yield of the artificial board in China exceeds 3.5 billion cubic meters in 2016, and the artificial board is stable in the first place in the world. At present, the adhesive commonly used in the production of artificial boards is formaldehyde synthetic resin, which is mainly urea-formaldehyde resin and modified products thereof, and the artificial boards, furniture, floors and other wooden products made of the artificial boards and the artificial boards made of the urea-formaldehyde resin adhesive can continuously release formaldehyde, pollute the indoor air environment, harm the health of people, and have become a hot spot of high social concern. In recent years, the production technology level of artificial boards in China is greatly improved, and a lot of research work is done on the aspect of reducing the formaldehyde emission of the artificial boards, such as: the formaldehyde emission of the artificial board is reduced to a certain extent by the measures or methods of reducing the molar ratio of formaldehyde, adding resorcinol, melamine modification, formaldehyde scavenger and the like, reducing the free formaldehyde content of the urea-formaldehyde resin, or adopting active molecules such as ammonia gas, ozone and the like which are easy to be combined with formaldehyde to carry out aftertreatment on the artificial board, but the formaldehyde emission of the artificial board and the wood product thereof cannot be fundamentally solved. The main reasons are as follows: as long as formaldehyde or other toxic chemical raw materials are used in the raw materials of the prepared resin adhesive, the product inevitably contains harmful gases such as formaldehyde, and the like, and the modification is temporary solution and permanent solution. The raw materials of the existing formaldehyde resin adhesives for artificial boards are all from petrochemical resources. With the concern of non-renewable petrochemical resources and the pursuit of green ecological environment of human beings, the sustainable development has attracted social wide attention, how to utilize biomass resources to develop high-quality environment-friendly bio-based adhesives has become a research hotspot and development trend in the field of artificial board adhesives in recent years, wherein the soybean protein adhesives prepared by taking nontoxic soybean protein as a raw material are important biomass adhesives, since the last 80 th century, a great deal of research work related to the soybean protein adhesives is carried out at home and abroad, and remarkable progress is made, and the partially modified soybean protein adhesives are reported to have been industrially popularized and applied on artificial board products such as plywood.
Due to the fact that the soybean protein is large in molecular weight and complex in structure and components, great difficulty is brought to chemical modification or modification of protein molecules, the qualified water-resistant cementing property of the soybean protein adhesive cannot be completely guaranteed through conventional modification treatment, and the water resistance and the cementing strength of the soybean protein adhesive can be remarkably improved through a method of enhancing modification by using a cross-linking agent. The crosslinking agent for modifying the soybean protein can be added in the preparation process of the adhesive or can be directly blended with the soybean protein before use. Commonly used effective crosslinking agents include various glycidyl ethers, epoxides, epoxy resins, etc. containing epoxy groups, various isocyanates containing isocyanate groups, acrylic or acrylamide compounds, and various aldehydes and their derivatives such as methylol urea, sodium formaldehyde disulfide, glutaraldehyde, glyoxal, glyceraldehyde, urea-formaldehyde, phenol-formaldehyde, methylol phenol, etc.
The composite crosslinking agent used in the invention patent with application number 201210277994.2 contains polyvinyl alcohol, isocyanate and amide polymers. The crosslinking agent of the invention of application No. 201210381979.2 is polymethylene polyphenyl isocyanate. The crosslinking agent in the invention patent with the application number of 201310336430.6 is melamine-formaldehyde resin, the invention patent with the application number of 201610372058.8 adopts aldehyde derivative resin (tannin-resorcinol-glutaraldehyde prepolymer) as the crosslinking agent, and the invention patent with the application number of 201210480566.X adopts glutaraldehyde as the crosslinking agent. According to the prior patent technologies and literature reports, most of the currently adopted crosslinking agents take nonrenewable petrochemical derivatives as raw materials, complete greenization and renewability of the soybean protein adhesive are not realized, and the crosslinking agents take aldehydes and derivatives thereof, isocyanate substances and other macromolecules as the crosslinking agents, so that the pollution problem of volatile harmful substances such as free aldehydes, benzene series and the like is brought to the soybean protein adhesive and glued artificial boards thereof.
Therefore, it is necessary to invent an aldehyde-free soy protein powder adhesive and a preparation method and application thereof.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides an aldehyde-free soybean protein powder adhesive and a preparation method and application thereof, plant protein and lignin epoxidation modified substance powder are used as main raw materials, the raw materials belong to renewable resources and have a wide range of requirements on protein content, the raw materials are wide in source, the raw materials do not contain benzene and formaldehyde substances, the prepared plant protein adhesive does not have the problem of formaldehyde release when used for manufacturing artificial boards, the operation is simple when the adhesive is used, a proper amount of the liquid adhesive can be prepared by adding the aldehyde-free soybean protein powder adhesive according to the required viscosity or solid content, the preparation and the use are convenient, and the problems in the background art are solved.
In order to achieve the purpose, the invention provides the following technical scheme: an aldehyde-free soy protein powder adhesive and a preparation method thereof, comprises the aldehyde-free soy protein powder adhesive, wherein the used main materials comprise the following components in percentage by weight: 35-45 parts of vegetable protein, 2-10 parts of lignin epoxidation modified substance powder and 0.6-1.5 parts of an activating agent, and the balance of auxiliary materials, wherein the auxiliary materials comprise a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is 5-10: the preparation method of the adhesive comprises the following specific operation steps:
the method comprises the following steps: preparing vegetable protein, an activating agent, a filler and a thickening agent according to a proportion, and preparing lignin epoxidation modified substance powder by using lignin, water, a modifying agent and an alkaline catalyst for later use;
step two: mixing the prepared vegetable protein, lignin epoxidation modified substance powder and an activating agent, and then putting into a stirrer for homogenization treatment to prepare a semi-finished product of the formaldehyde-free soybean protein powder adhesive;
step three: measuring the total mass of the vegetable protein raw material, calculating the adding amount of the filler and the thickening agent, measuring the filler and the thickening agent in the measured value, adding the filler and the thickening agent into the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and uniformly mixing to prepare the formaldehyde-free soybean protein powder adhesive;
step four: and filling the prepared formaldehyde-free soybean protein powder adhesive, sealing and storing in a cool and dry place.
Preferably, the vegetable protein is one or a mixture of several of defatted soybean flour, defatted soybean meal, soybean flour, soybean protein isolate, soybean protein concentrate or defatted peanut flour.
Preferably, the activating agent is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, guanidine hydrochloride, urea, sodium sulfite, sodium bisulfite and sodium borate.
Preferably, the filler is one or a mixture of more of flour, bark powder, calcium carbonate, pottery clay, calcium chloride, talcum powder or nut shell powder, and the thickener is corn starch.
Preferably, in the preparation of the lignin epoxidation modified product powder in the first step, the lignin is set as enzymatic hydrolysis lignin, the modifier is set as epichlorohydrin, the alkaline catalyst is set as sodium hydroxide, and the volume ratio of the lignin, water, the modifier and the alkaline catalyst is set as lignin: water: modifying agent: basic catalyst ═ 5: 8: 10: the preparation method comprises the following steps:
a) adjusting the pH value: putting water into a reaction kettle, adjusting the pH value to 7.5-10, and adding lignin;
b) one round of reaction: stirring uniformly, adding a modifier, heating to 30-80 ℃, reacting for 1-3h under the condition of heat preservation, and adding an alkaline catalyst;
c) carrying out two-round reaction: reacting at 30-80 deg.C for 0.5-3h, cooling to 30 deg.C, and discharging to obtain lignin modified substance with epoxy group;
d) powder preparation: spray drying the modified product to obtain lignin epoxidized modified product powder.
Preferably, the protein content in the aldehyde-free soy protein powder adhesive prepared in the third step is not lower than 38%, and the calculation formula in the step is as follows:
Figure BDA0002290733850000041
wherein, Z is the content of pure protein, Y is the total amount of the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and X is the total amount of the filler and the thickening agent.
Preferably, the aldehyde-free soy protein powder adhesive is used for preparing an aldehyde-free soy protein liquid adhesive, the aldehyde-free soy protein liquid adhesive is used for bonding an artificial board, and the using method comprises the following steps:
the method comprises the following steps: firstly, mixing an aldehyde-free soybean protein powder adhesive with water to prepare a liquid adhesive, wherein the weight ratio of the powder adhesive is as follows: water mass ratio 42-50: 60, uniformly stirring to obtain a liquid aldehyde-free soy protein adhesive when no granular glue powder exists;
step two: adding water into the formaldehyde-free soy protein adhesive prepared in the step one again to prepare a mixed solution with the solid content of 50-70%;
step three: and (3) coating the mixed solution on the wood material by using a spraying mode, and gluing the wood material with the plate to prepare the wood composite material.
Preferably, another application of the aldehyde-free soy protein powder binder is also included, in which the aldehyde-free soy protein powder is mixed directly into the vegetable fiber shaving material in powder form to make a particle board.
The invention has the technical effects and advantages that:
1. the vegetable protein and lignin epoxy modified powder is adopted as the main raw material, the raw material source is wide, the raw material does not contain benzene and formaldehyde substances, the prepared vegetable protein adhesive does not have the problem of formaldehyde release when being used for manufacturing artificial boards, the operation is simple when the adhesive is used, and the liquid adhesive can be prepared by adding a proper amount into the formaldehyde-free soybean protein powder adhesive according to the required viscosity or solid content, so that the preparation and the use are convenient;
2. the epoxy modified lignin contains a large amount of active epoxy groups, and a rigid benzene ring structure contained in the lignin has good water resistance, so that in the high-temperature hot-pressing process, the epoxy groups and amino groups, carboxyl groups and the like of the soybean protein generate ring-opening crosslinking reaction, a lignin macromolecular structure is introduced into a soybean protein adhesive system, an insoluble macromolecular solidified body with a water-resistant structure is formed, and the soybean protein adhesive is endowed with good adhesive strength and water resistance. Meanwhile, when the formaldehyde-free soybean protein powder adhesive is used for adhering artificial boards, inorganic fillers such as calcium carbonate, argil, calcium chloride, talcum powder and the like contained in the adhesive can fill tiny pores generated in a solidified adhesive layer due to water vapor discharge during the adhesive solidification reaction, so that a compact adhesive layer structure is formed, and the water-resistant adhesion performance of the protein adhesive is further improved.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides an aldehyde-free soybean protein powder adhesive and a preparation method thereof, wherein the aldehyde-free soybean protein powder adhesive comprises the following main materials in parts by weight: 35 parts of vegetable protein, 2 parts of lignin epoxidation modified substance powder and 0.6 part of an activating agent, and the balance of auxiliary materials, wherein the auxiliary materials comprise a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is set as 5: the preparation method of the adhesive comprises the following specific operation steps:
the method comprises the following steps: preparing plant protein, an activating agent, a filler and a thickening agent according to a proportion, and preparing lignin epoxidation modified substance powder by using lignin, water, a modifying agent and an alkaline catalyst, wherein the plant protein is a raw material containing the plant protein and comprises soybean protein, the soybean protein is prepared from defatted soybean powder, defatted soybean meal, soybean powder, soybean protein isolate, soybean protein concentrate, defatted peanut powder or other biomass raw materials with the protein content of not less than 30% and processing residues thereof, the plant protein is processed into powder by grinding, the particle size of the plant protein powder is set to be 30 meshes, specifically the defatted soybean meal powder, the activating agent is specifically set to be 0.3 part of sodium bisulfite and 0.3 part of sodium borate, the lignin epoxidation modified substance is a compound containing epoxy groups or a macromolecule and is subjected to ring-opening reaction of the epoxy groups with hydroxyl and carboxyl groups on macromolecules of the lignin, forming a lignin modifier with an epoxy group;
in the preparation of the lignin epoxidation modified substance powder, the lignin is set as enzymolysis lignin, the modifier is set as epichlorohydrin, the alkaline catalyst is set as sodium hydroxide, and the volume ratio of the lignin, water, the modifier and the alkaline catalyst is set as lignin: water: modifying agent: basic catalyst ═ 5: 8: 10: the preparation method comprises the following steps:
a) adjusting the pH value: putting water into a reaction kettle, adjusting the pH value to 7.5-10, and adding lignin;
b) one round of reaction: stirring uniformly, adding a modifier, heating to 30-80 ℃, reacting for 1-3h under the condition of heat preservation, and adding an alkaline catalyst;
c) carrying out two-round reaction: reacting at 30-80 deg.C for 0.5-3h, cooling to 30 deg.C, and discharging to obtain lignin modified substance with epoxy group;
d) powder preparation: spray drying the modified product to obtain lignin epoxidized modified product powder.
Step two: putting the prepared vegetable protein, lignin epoxidation modified substance powder and an activating agent into a stirrer to be uniformly mixed to prepare a semi-finished product of the formaldehyde-free soybean protein powder adhesive;
step three: measuring the total mass of the vegetable protein raw materials, calculating the adding amount of a filler and a thickening agent, wherein the filler is specifically made of argil, the thickening agent is corn starch, the filler and the thickening agent in the measured value are measured and added into a semi-finished product of the formaldehyde-free soybean protein powder adhesive and are uniformly mixed to prepare the formaldehyde-free soybean protein powder adhesive, the protein content in the formaldehyde-free soybean protein powder adhesive is not lower than 38%, and the calculation formula in the step is specifically as follows:
wherein Z is the content of pure protein, Y is the total amount of the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and X is the total amount of the filler and the thickening agent;
step four: and filling the prepared formaldehyde-free soybean protein powder adhesive, sealing and storing in a cool and dry place.
The application of the aldehyde-free soybean protein powder adhesive is used for preparing the aldehyde-free soybean protein liquid adhesive, the aldehyde-free soybean protein liquid adhesive is used for bonding artificial boards, and the application method comprises the following steps:
the method comprises the following steps: firstly, mixing an aldehyde-free soybean protein powder adhesive with water to prepare a liquid adhesive, wherein the weight ratio of the powder adhesive is as follows: water mass ratio 42: 60, uniformly stirring to obtain a liquid aldehyde-free soy protein adhesive when no granular glue powder exists;
step two: adding water into the formaldehyde-free soy protein adhesive prepared in the step one again to prepare a mixed solution with the solid content of 50%;
step three: and (3) coating the mixed solution on the wood material by using a spraying mode, and gluing the wood material with the plate to prepare the wood composite material.
Further, another application of the aldehyde-free soy protein powder binder is included, in which the aldehyde-free soy protein powder is mixed directly into the vegetable fiber shaving material in powder form to prepare a particle board.
The formaldehyde-free soy protein powder adhesive prepared in the embodiment is yellow powder particles, has the fineness of 100-350 meshes, has good dispersibility and fluidity after being dissolved in water, is easy to use, can be conveniently prepared into the formaldehyde-free soy protein adhesive, and has good viscosity, in addition, the performance test is carried out on the prepared adhesive in the technical scheme, the bonding use test is carried out on the adhesive, and the result shows that: the viscosity of the formaldehyde-free soybean protein adhesive is set to 18792MPa s at 25 ℃, the active period after glue mixing is 13.5h, the content of free benzene compounds is 0, the content of free formaldehyde is 0, the adhesive is completely green, and the adhesive can be preparedThe green environment-friendly plywood without harmful substance release has the advantages that after the adhesive is bonded with the wood board, the bonding strength is 1.06MPa, the formaldehyde release amount is 0.03mg/L, and the total volatile organic compound content is 0.06mg/m for 72h2H, the plywood made of the prepared soy protein adhesive has extremely low trace formaldehyde release, which is caused by the fact that wood releases formaldehyde, and the value of the total volatile organic compound release rate is extremely low and is close to the formaldehyde release value, which shows that the prepared plywood has no other toxic and harmful organic matters to release except the ultralow formaldehyde released by the wood.
Example 2:
the invention provides an aldehyde-free soybean protein powder adhesive and a preparation method thereof, wherein the aldehyde-free soybean protein powder adhesive comprises the following main materials in parts by weight: 40 parts of vegetable protein, 6 parts of lignin epoxidized modifier powder and 1.0 part of an activator, and the balance is an auxiliary material, wherein the auxiliary material consists of a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is set as 8: the preparation method of the adhesive comprises the following specific operation steps:
the method comprises the following steps: preparing plant protein, an activating agent, a filler and a thickening agent according to a proportion, and preparing lignin epoxidation modified substance powder by using lignin, water, a modifying agent and an alkaline catalyst, wherein the plant protein is a raw material containing the plant protein and comprises soybean protein, the soybean protein is prepared from defatted soybean powder, defatted soybean meal, soybean powder, soybean protein isolate, soybean protein concentrate, defatted peanut powder or other biomass raw materials with the protein content of not less than 30% and processing residues thereof, the plant protein is processed into powder by grinding, the particle size of the plant protein powder is set to be 80 meshes, specifically the defatted soybean meal powder, the activating agent is specifically set to be 0.7 part of sodium bisulfite and 0.3 part of sodium borate, the lignin epoxidation modified substance is a compound containing epoxy groups or a macromolecule and is subjected to ring-opening reaction of the epoxy groups with hydroxyl and carboxyl groups on macromolecules of the lignin, forming a lignin modifier with an epoxy group;
in the preparation of the lignin epoxidation modified substance powder, the lignin is set as enzymolysis lignin, the modifier is set as epichlorohydrin, the alkaline catalyst is set as sodium hydroxide, and the volume ratio of the lignin, water, the modifier and the alkaline catalyst is set as lignin: water: modifying agent: basic catalyst ═ 5: 8: 10: the preparation method comprises the following steps:
a) adjusting the pH value: putting water into a reaction kettle, adjusting the pH value to 7.5-10, and adding lignin;
b) one round of reaction: stirring uniformly, adding a modifier, heating to 30-80 ℃, reacting for 1-3h under the condition of heat preservation, and adding an alkaline catalyst;
c) carrying out two-round reaction: reacting at 30-80 deg.C for 0.5-3h, cooling to 30 deg.C, and discharging to obtain lignin modified substance with epoxy group;
d) powder preparation: spray drying the modified product to obtain lignin epoxidized modified product powder.
Step two: putting the prepared vegetable protein, lignin epoxidation modified substance powder and an activating agent into a stirrer to be uniformly mixed to prepare a semi-finished product of the formaldehyde-free soybean protein powder adhesive;
step three: measuring the total mass of the vegetable protein raw materials, calculating the adding amount of a filler and a thickening agent, wherein the filler is specifically made of argil, the thickening agent is corn starch, the filler and the thickening agent in the measured value are measured and added into a semi-finished product of the formaldehyde-free soybean protein powder adhesive and are uniformly mixed to prepare the formaldehyde-free soybean protein powder adhesive, the protein content in the formaldehyde-free soybean protein powder adhesive is not lower than 38%, and the calculation formula in the step is specifically as follows:
Figure BDA0002290733850000091
wherein Z is the content of pure protein, Y is the total amount of the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and X is the total amount of the filler and the thickening agent;
step four: and filling the prepared formaldehyde-free soybean protein powder adhesive, sealing and storing in a cool and dry place.
The application of the aldehyde-free soybean protein powder adhesive is used for preparing the aldehyde-free soybean protein liquid adhesive, the aldehyde-free soybean protein liquid adhesive is used for bonding artificial boards, and the application method comprises the following steps:
the method comprises the following steps: firstly, mixing an aldehyde-free soybean protein powder adhesive with water to prepare a liquid adhesive, wherein the weight ratio of the powder adhesive is as follows: water mass ratio 46: 60, uniformly stirring to obtain a liquid aldehyde-free soy protein adhesive when no granular glue powder exists;
step two: adding water into the formaldehyde-free soy protein adhesive prepared in the step one again to prepare a mixed solution with a solid content of 60%;
step three: and (3) coating the mixed solution on the wood material by using a spraying mode, and gluing the wood material with the plate to prepare the wood composite material.
Further, another application of the aldehyde-free soy protein powder binder is included, in which the aldehyde-free soy protein powder is mixed directly into the vegetable fiber shaving material in powder form to prepare a particle board.
In addition, in the technical scheme, performance test is performed on the prepared adhesive, and bonding use test is performed on the adhesive, and the result shows that: the viscosity of the formaldehyde-free soybean protein adhesive is set to 19273MPa & s at 25 ℃, the active period after glue mixing is 15h, the content of free benzene compounds is 0, the content of free formaldehyde is 0, the adhesive is completely green, and the green environment-friendly plywood without harmful substance release of the plywood can be manufactured, after the adhesive is bonded to a wood board, the bonding strength is 1.28MPa, the formaldehyde release amount is 0.02mg/L, and the total volatile organic compound 72h is 0.06mg/m2H, the plywood made of the prepared soy protein adhesive has extremely low trace formaldehyde release, which is caused by the release of formaldehyde from wood, and the value of the total volatile organic compound release rate is extremely low and is close to the formaldehyde release value, which indicates that the prepared plywood has super-high formaldehyde release rate except for the release of the woodBesides low formaldehyde, no other toxic and harmful organic substances are released.
Example 3:
the invention provides an aldehyde-free soybean protein powder adhesive and a preparation method thereof, wherein the aldehyde-free soybean protein powder adhesive comprises the following main materials in parts by weight: 45 parts of vegetable protein, 10 parts of lignin epoxidized modifier powder and 1.5 parts of an activating agent, and the balance is auxiliary materials, wherein the auxiliary materials comprise a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is 10: the preparation method of the adhesive comprises the following specific operation steps:
the method comprises the following steps: preparing plant protein, an activating agent, a filler and a thickening agent according to a proportion, and preparing lignin epoxidation modified substance powder by using lignin, water, a modifying agent and an alkaline catalyst, wherein the plant protein is a raw material containing the plant protein and comprises soybean protein, the soybean protein is prepared from defatted soybean powder, defatted soybean meal, soybean powder, soybean protein isolate, soybean protein concentrate, defatted peanut powder or other biomass raw materials with the protein content of not less than 30% and processing residues thereof, the plant protein is processed into powder by grinding, the particle size of the plant protein powder is set to be 100 meshes, specifically the defatted soybean meal powder, the activating agent is specifically set to be 1.0 part of sodium bisulfite and 0.5 part of sodium borate, the lignin epoxidation modified substance is a compound containing epoxy groups or a macromolecule and is subjected to ring-opening reaction of the epoxy groups with hydroxyl and carboxyl groups on macromolecules of the lignin, forming a lignin modifier with an epoxy group;
in the preparation of the lignin epoxidation modified substance powder, the lignin is set as enzymolysis lignin, the modifier is set as epichlorohydrin, the alkaline catalyst is set as sodium hydroxide, and the volume ratio of the lignin, water, the modifier and the alkaline catalyst is set as lignin: water: modifying agent: basic catalyst ═ 5: 8: 10: the preparation method comprises the following steps:
a) adjusting the pH value: putting water into a reaction kettle, adjusting the pH value to 7.5-10, and adding lignin;
b) one round of reaction: stirring uniformly, adding a modifier, heating to 30-80 ℃, reacting for 1-3h under the condition of heat preservation, and adding an alkaline catalyst;
c) carrying out two-round reaction: reacting at 30-80 deg.C for 0.5-3h, cooling to 30 deg.C, and discharging to obtain lignin modified substance with epoxy group;
d) powder preparation: spray drying the modified product to obtain lignin epoxidized modified product powder.
Step two: putting the prepared vegetable protein, lignin epoxidation modified substance powder and an activating agent into a stirrer to be uniformly mixed to prepare a semi-finished product of the formaldehyde-free soybean protein powder adhesive;
step three: measuring the total mass of the vegetable protein raw materials, calculating the adding amount of a filler and a thickening agent, wherein the filler is specifically made of argil, the thickening agent is corn starch, the filler and the thickening agent in the measured value are measured and added into a semi-finished product of the formaldehyde-free soybean protein powder adhesive and are uniformly mixed to prepare the formaldehyde-free soybean protein powder adhesive, the protein content in the formaldehyde-free soybean protein powder adhesive is not lower than 38%, and the calculation formula in the step is specifically as follows:
Figure BDA0002290733850000121
wherein Z is the content of pure protein, Y is the total amount of the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and X is the total amount of the filler and the thickening agent;
step four: and filling the prepared formaldehyde-free soybean protein powder adhesive, sealing and storing in a cool and dry place.
The application of the aldehyde-free soybean protein powder adhesive is used for preparing the aldehyde-free soybean protein liquid adhesive, the aldehyde-free soybean protein liquid adhesive is used for bonding artificial boards, and the application method comprises the following steps:
the method comprises the following steps: firstly, mixing an aldehyde-free soybean protein powder adhesive with water to prepare a liquid adhesive, wherein the weight ratio of the powder adhesive is as follows: water mass ratio of 50: 60, uniformly stirring to obtain a liquid aldehyde-free soy protein adhesive when no granular glue powder exists;
step two: adding water into the formaldehyde-free soy protein adhesive prepared in the step one again to prepare a mixed solution with the solid content of 70%;
step three: and (3) coating the mixed solution on the wood material by using a spraying mode, and gluing the wood material with the plate to prepare the wood composite material.
Further, another application of the aldehyde-free soy protein powder binder is included, in which the aldehyde-free soy protein powder is mixed directly into the vegetable fiber shaving material in powder form to prepare a particle board.
Comparing examples 1 and 2, the formaldehyde-free soy protein powder adhesive prepared in this example is yellow powder particles with a fineness of 100-350 mesh, has good dispersibility and fluidity after being dissolved in water, is easy to use, can be conveniently prepared into a formaldehyde-free soy protein adhesive, and has good viscosity, in addition, the performance test is performed on the prepared adhesive in the technical scheme, and the bonding use test is performed on the adhesive, and the result shows that: the viscosity of the formaldehyde-free soybean protein adhesive is set to 19258MPa & s at 25 ℃, the active period after glue mixing is 14.5h, the content of free benzene compounds is 0, the content of free formaldehyde is 0, the adhesive is completely green, and the green environment-friendly plywood without harmful substance release of the plywood can be manufactured, after the adhesive is bonded to the wood board, the bonding strength is 1.19MPa, the formaldehyde release amount is 0.03mg/L, and the total volatile organic compound 72h is 0.07mg/m2H, the plywood made of the prepared soy protein adhesive has extremely low trace formaldehyde release, which is caused by the fact that wood releases formaldehyde, and the value of the total volatile organic compound release rate is extremely low and is close to the formaldehyde release value, which shows that the prepared plywood has no other toxic and harmful organic matters to release except the ultralow formaldehyde released by the wood.
Tables 1-2 are derived from examples 1-3:
table 1 adhesive performance test index
Figure BDA0002290733850000131
Table 2 adhesive bonding sheet performance test index
Figure BDA0002290733850000132
From tables 1-2, it can be seen that in example 2, the raw material ratio is moderate, the processing technique is most suitable for the preparation of the aldehyde-free soy protein powder adhesive, lignin from nature is used as the main raw material, a lignin modifier containing a certain epoxy group is generated through the ring-opening polymerization reaction of hydroxyl on the lignin and a compound containing an epoxy group or an oxygen-containing group on an aqueous polymer, and the lignin modifier with high activity is used as a cross-linking agent to generate the cross-linking reaction with soy protein molecules during high-temperature hot pressing, so as to form an adhesive curing system with a water-resistant structure, so that the adhesive has the advantages of excellent bonding performance, good water resistance, low production cost, long storage period, convenient transportation and use, convenient packaging and transportation of the aldehyde-free soy protein powder adhesive, and solves the problems that the soy protein adhesive is easy to decay and has a short sale radius, compared with a transportation liquid adhesive (the solid content is, the transportation cost of the effective content of the adhesive is also reduced. The adopted raw materials are vegetable proteins, belong to renewable resources, have a wide range of requirements on protein content, have wide sources of raw materials, contain no benzene and formaldehyde substances in the raw materials, and the prepared vegetable protein adhesive does not have the problem of formaldehyde release when used for manufacturing artificial boards.
Finally, it should be noted that: 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 are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.

Claims (9)

1. An aldehyde-free soy protein powder adhesive and a preparation method thereof, comprises the aldehyde-free soy protein powder adhesive, wherein the used main materials comprise the following components in percentage by weight: 35-45 parts of vegetable protein, 2-10 parts of lignin epoxidation modified substance powder and 0.6-1.5 parts of an activating agent, and the balance of auxiliary materials, wherein the auxiliary materials comprise a filler and a thickening agent, and the mass ratio of the filler to the thickening agent is 5-10: 1, characterized in that: the preparation method of the adhesive comprises the following specific operation steps:
the method comprises the following steps: preparing vegetable protein, an activating agent, a filler and a thickening agent according to a proportion, and preparing lignin epoxidation modified substance powder by using lignin, water, a modifying agent and an alkaline catalyst for later use;
step two: mixing the prepared vegetable protein, lignin epoxidation modified substance powder and an activating agent, and then putting into a stirrer for homogenization treatment to prepare a semi-finished product of the formaldehyde-free soybean protein powder adhesive;
step three: measuring the total mass of the vegetable protein raw material, calculating the adding amount of the filler and the thickening agent, measuring the filler and the thickening agent in the measured value, adding the filler and the thickening agent into the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and uniformly mixing to prepare the formaldehyde-free soybean protein powder adhesive;
step four: and filling the prepared formaldehyde-free soybean protein powder adhesive, sealing and storing in a cool and dry place.
2. The aldehyde-free soy protein powder adhesive and the preparation method thereof as claimed in claim 1, wherein: the vegetable protein is one or more of defatted soybean flour, defatted soybean meal, soybean flour, soybean protein isolate, soybean protein concentrate or defatted peanut powder.
3. The aldehyde-free soy protein powder adhesive and the preparation method thereof as claimed in claim 1, wherein: the activating agent is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, guanidine hydrochloride, urea, sodium sulfite, sodium bisulfite and sodium borate.
4. The aldehyde-free soy protein powder adhesive and the preparation method thereof as claimed in claim 1, wherein: the filler is one or a mixture of more of flour, bark powder, calcium carbonate, pottery clay, calcium chloride, talcum powder or nut shell powder, and the thickener is corn starch.
5. The aldehyde-free soy protein powder adhesive and the preparation method thereof as claimed in claim 1, wherein: in the preparation of the lignin epoxidation modified product powder in the first step, the lignin is set as enzymolysis lignin, the modifier is set as epichlorohydrin, the alkaline catalyst is set as sodium hydroxide, and the volume ratio of the lignin, the water, the modifier and the alkaline catalyst is set as lignin: water: modifying agent: basic catalyst ═ 5: 8: 10: the preparation method comprises the following steps:
a) adjusting the pH value: putting water into a reaction kettle, adjusting the pH value to 7.5-10, and adding lignin;
b) one round of reaction: stirring uniformly, adding a modifier, heating to 30-80 ℃, reacting for 1-3h under the condition of heat preservation, and adding an alkaline catalyst;
c) carrying out two-round reaction: reacting at 30-80 deg.C for 0.5-3h, cooling to 30 deg.C, and discharging to obtain lignin modified substance with epoxy group;
d) powder preparation: spray drying the modified product to obtain lignin epoxidized modified product powder.
6. The aldehyde-free soy protein powder adhesive and the preparation method thereof as claimed in claim 1, wherein: the protein content in the formaldehyde-free soybean protein powder adhesive prepared in the third step is not lower than 38%, and a calculation formula in the step is as follows:
Figure FDA0002290733840000021
wherein, Z is the content of pure protein, Y is the total amount of the semi-finished product of the formaldehyde-free soybean protein powder adhesive, and X is the total amount of the filler and the thickening agent.
7. The application of the formaldehyde-free soy protein powder adhesive is characterized in that: the aldehyde-free soybean protein powder adhesive is used for preparing an aldehyde-free soybean protein liquid adhesive, and the aldehyde-free soybean protein liquid adhesive is used for bonding artificial boards.
8. The use of the aldehyde-free soy protein powder adhesive as claimed in claim 7, wherein: the application method of the aldehyde-free soybean protein powder adhesive comprises the following steps:
the method comprises the following steps: firstly, deionized water is used for preparing an aldehyde-free soybean protein powder adhesive into a liquid adhesive, and the weight ratio of the powder adhesive is as follows: deionized water with the mass ratio of 42-50: 60, uniformly stirring to obtain a liquid aldehyde-free soy protein adhesive when no granular glue powder exists;
step two: adding alcohol into the formaldehyde-free soy protein adhesive again to prepare a mixed solution with the solid content of 50-70%;
step three: and (3) coating the mixed solution on the wood material by using a spraying mode, and gluing the wood material with the plate to prepare the wood composite material.
9. The use of the aldehyde-free soy protein powder adhesive as claimed in claim 7, wherein: another application of the aldehyde-free soy protein powder binder is also included, in which the aldehyde-free soy protein powder is mixed directly into the vegetable fiber shaving material in powder form to make a particle board.
CN201911178881.5A 2019-11-27 2019-11-27 Formaldehyde-free soybean protein powder adhesive and preparation method and application thereof Pending CN110835518A (en)

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