CN111171256B - Modified isocyanate emulsion cross-linking agent, modified adhesive and application - Google Patents

Modified isocyanate emulsion cross-linking agent, modified adhesive and application Download PDF

Info

Publication number
CN111171256B
CN111171256B CN202010066314.7A CN202010066314A CN111171256B CN 111171256 B CN111171256 B CN 111171256B CN 202010066314 A CN202010066314 A CN 202010066314A CN 111171256 B CN111171256 B CN 111171256B
Authority
CN
China
Prior art keywords
parts
modified
protein
meal
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010066314.7A
Other languages
Chinese (zh)
Other versions
CN111171256A (en
Inventor
张世锋
李智
郭永胜
金太权
余养伦
刘红光
李建章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Forestry University
Original Assignee
Beijing Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Forestry University filed Critical Beijing Forestry University
Priority to CN202010066314.7A priority Critical patent/CN111171256B/en
Publication of CN111171256A publication Critical patent/CN111171256A/en
Application granted granted Critical
Publication of CN111171256B publication Critical patent/CN111171256B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a modified isocyanate emulsion cross-linking agent, a modified adhesive and application thereof. The modified isocyanate cross-linking agent is prepared by polymerizing a modifying agent and isocyanate; wherein the modifier contains catechol groups. The embodiment of the invention also provides a modified plant protein adhesive prepared from the modified isocyanate emulsion cross-linking agent. According to the invention, the polyphenol substance containing catechol groups is polymerized with isocyanate, so that the stability of the isocyanate can be improved, and the isocyanate can be used for preparing the vegetable protein adhesive, so that the pre-pressing performance of the adhesive can be improved, and the water resistance and the bonding strength of the adhesive can be effectively enhanced.

Description

Modified isocyanate emulsion cross-linking agent, modified adhesive and application
Technical Field
The invention relates to a vegetable protein adhesive, in particular to a modified isocyanate emulsion cross-linking agent, a modified adhesive and application.
Background
The plant protein adhesive is used as a trialdehyde adhesive to effectively replace the trialdehyde adhesive, and has the advantages of no formaldehyde release, abundant sources, simple preparation process and the like, thus becoming a research hot spot in the wood processing industry. The soybean protein, polysaccharide and the like have large molecular weight, and the viscosity of the adhesive is high after the soybean protein, the polysaccharide and the like are dissolved. In order to ensure good flowability of the adhesive, the solids content is generally low; therefore, the problem of poor pre-pressing forming performance is easily caused in the processing process, and the pre-pressing forming processing of the artificial board is not facilitated.
The emulsion cross-linking agent prepared by emulsifying isocyanate and water is added into the vegetable protein glue, so that the pre-pressing forming performance and the water-resistant gluing strength can be effectively improved. The high-reactivity isocyanate is used as an auxiliary crosslinking agent to modify the vegetable protein glue, and covalent crosslinking structures are formed among the isocyanate, the vegetable protein and the wood, so that the normal-temperature prepressing forming performance of the adhesive is remarkably improved. However, isocyanate reacts with water at normal temperature to generate carbon dioxide, the system is easy to foam, the pot life is short, and the industrial actual production needs are difficult to meet.
In order to improve the pot life of the isocyanate modified aqueous adhesives, a great deal of research has been conducted. The common modification method is to add filler into isocyanate or adopt a chemical end-capping method to improve the stability of the isocyanate, however, the conventional modification method has the problems of uneven dispersion, easy stress concentration of a glue layer, complex process and the like, and is limited in practical use. How to ensure the gluing performance and the pre-pressing forming performance of the adhesive at the same time, meets the production requirement, and becomes a main problem faced by the modified plant protein adhesive.
Disclosure of Invention
The inventor discovers that the stability of isocyanate can be improved by polymerizing polyphenol substances containing catechol groups with isocyanate, and the stability of the isocyanate can be improved when the polyphenol substances containing catechol groups are used for preparing the vegetable protein adhesive, so that the pre-pressing performance of the adhesive and the forming performance of the adhesive in the process of bonding a veneer with high water content can be improved, and meanwhile, the water resistance and bonding strength of the adhesive can be effectively enhanced.
The embodiment of the invention provides a modified isocyanate cross-linking agent, which is prepared by polymerizing a modifying agent and isocyanate.
In some embodiments of the invention, the modifier contains catechol groups.
In some embodiments of the invention, the modifier is a polyphenol, such as a plant polyphenol, that contains catechol groups.
In some embodiments of the invention, the modifier is selected from one or more of tannic acid, tannins, tea polyphenols, gallic acid, and the like.
In some embodiments of the invention, the isocyanate is selected from one or more of polydiphenylmethane diisocyanate (pMDI), isophorone diisocyanate (IPDI), triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanate, TDI-trimethylpropane adduct, and the like.
In some embodiments of the invention, the isocyanate is polydiphenylmethane diisocyanate (pMDI) in which the-NCO group content is 31.6%.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (2-8): 20.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (3.5-5): 20.
In some embodiments of the invention, the weight ratio of modifier to isocyanate is (4-5): 20.
In some embodiments of the invention, the modified isocyanate crosslinking agent is prepared by polymerizing a modifier and an isocyanate in the presence of water. In some embodiments of the invention, the weight ratio of water to isocyanate is (5-15): 20, preferably (6-8): 20.
In some embodiments of the invention, the modified isocyanate crosslinker is an emulsion.
The embodiment of the invention also provides a modified isocyanate emulsion cross-linking agent which is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
5-15 Parts of water
2-8 Parts of modifier
In some embodiments of the present invention, the modified isocyanate emulsion crosslinker is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 Parts of water
3.5-5 Parts of modifier
In some embodiments of the present invention, the modified isocyanate emulsion crosslinker is prepared from the following raw materials in parts by weight:
isocyanate 20 parts
6-8 Parts of water
4-5 Parts of modifier
In some embodiments of the invention, the isocyanate, the modifier in the modified isocyanate emulsion crosslinker described above are as defined above.
The modified isocyanate crosslinking agent and the modified isocyanate emulsion crosslinking agent provided by the embodiment of the invention have the advantages of high stability and good reactivity, and can improve the prepressing forming performance, the water resistance and the bonding strength when the plant protein adhesive is used for bonding the high-water-content veneer. In addition, the preparation process has the advantages of simplicity and convenience.
The embodiment of the invention also provides a preparation method of the modified isocyanate cross-linking agent, which comprises the step of polymerizing the modified agent with isocyanate. In some embodiments, the polymerization is performed in the presence of water.
The embodiment of the invention also provides a preparation method of the modified isocyanate emulsion cross-linking agent, which comprises the following steps:
1) Providing an aqueous modifier solution;
2) The aqueous modifier solution is mixed with isocyanate and the modifier is polymerized with isocyanate.
Wherein,
The modifier aqueous solution in the step 1) is prepared from the modifier and water. The modifier may be added to water (e.g., 50-80 ℃ hot water; 60 ℃ hot water in some embodiments) and stirred until uniformly mixed, e.g., 5-10 minutes (or 6 minutes). Mechanical stirring may be used for mixing, for example, at 600-1200 rpm.
In some embodiments, step 2) further comprises the step of emulsifying after mixing the aqueous modifier solution with the isocyanate. The emulsion cross-linking agent with uniform texture can be prepared by uniformly mixing the modifier aqueous solution and the oily isocyanate matrix through emulsification.
In some embodiments, step 2) may be emulsified using an emulsifying machine for a period of time ranging from 5 to 15 minutes, for example 8 minutes.
The invention also comprises the modified isocyanate emulsion cross-linking agent prepared by the method.
The invention also provides application of the modified isocyanate crosslinking agent or the modified isocyanate emulsion crosslinking agent in preparation of the vegetable protein adhesive. Experiments show that the vegetable protein adhesive prepared from the modified isocyanate crosslinking agent and the modified isocyanate emulsion crosslinking agent has the advantages of higher bonding strength, good water resistance, no formaldehyde release, good pre-pressing forming performance and the like.
The invention also provides a modified plant protein adhesive which is prepared from the following raw materials in parts by weight:
in some embodiments of the invention, the protein meal is a vegetable protein meal.
In some embodiments of the present invention, the protein meal is one or more of soybean meal, maple meal, peanut meal, castor meal, cottonseed meal, rapeseed meal, distillers' grains, and the like.
In some embodiments of the invention, the protein meal has a particle size of 70-500 mesh.
In some embodiments of the invention, the protein meal has a particle size of 100-400 mesh.
In some embodiments of the invention, the protein meal has a particle size of 200-250 mesh.
The protein meal in the particle size range is powdery, and the powder is easy to disperse and is beneficial to fully contact and reaction with the cross-linking agent.
In some embodiments of the invention, the protein meal is defatted protein meal.
In some embodiments of the invention, the protein content in the protein meal is above 40 wt%.
In some embodiments of the invention, the protein meal has a protein content of 40-60wt%.
In some embodiments of the invention, the protein meal has a protein content of 43wt%.
In some embodiments of the present invention, the curing agent is a glycidyl ether, for example, one or more crosslinking agents selected from polyamide polyamine epichlorohydrin resin (PAE), epoxy diluent glycerol triglycidyl ether (PTGE), ethylene glycol diglycidyl ether (EDGE), and the like, preferably PTGE.
In some embodiments of the present invention, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
in some embodiments of the present invention, the modified vegetable protein adhesive is prepared from the following raw materials in parts by weight:
in some embodiments of the present invention, the preparation method of the vegetable protein adhesive includes the following steps:
a) Providing a mixed solution containing protein meal and water;
b) And mixing the mixed solution containing the protein meal and water with the modified isocyanate emulsion cross-linking agent and the curing agent to prepare the modified plant protein adhesive.
Wherein, step a) can add the raw materials of the protein meal into water under the condition of stirring, stir evenly; preparing a mixed solution containing protein meal and water.
And b) adding the modified isocyanate emulsion cross-linking agent and the curing agent into the mixed solution containing the protein meal and the water, and stirring to obtain the modified plant protein adhesive.
In some embodiments of the invention, steps a) and b) may be carried out by mechanical stirring, for example at a speed of 600-1200 rpm.
The invention also comprises application of the modified plant protein adhesive in the fields of wood, bamboo, furniture, printed matters, buildings, decoration and the like.
In particular, the invention also comprises wood processed products and bamboo processed products containing the modified plant protein adhesive, such as artificial boards of plywood, chipboard, medium-density fiberboard, joinery board and the like.
The preparation method of the modified isocyanate emulsion cross-linking agent adopts a method of directly emulsifying isocyanate and aqueous solution, and the plant polyphenol is added into water to be uniformly mixed and then is emulsified with the isocyanate, so that the distribution of the modified isocyanate emulsion cross-linking agent is more uniform and the operation is simple.
The preparation method of the modified plant protein adhesive adopts a physical blending method, firstly, protein meal is dispersed into water, unmodified plant protein adhesive is obtained after uniform stirring, then the modified isocyanate emulsion cross-linking agent and the curing agent are added into the plant protein adhesive, and the modified plant protein adhesive is obtained after uniform stirring. In the obtained vegetable protein glue, the isocyanate emulsion cross-linking agent and the curing agent are uniformly dispersed and tightly combined with protein molecules.
The modified protein adhesive prepared by the embodiment of the invention has no formaldehyde release, and the manufactured artificial board has no formaldehyde release problem; the adhesive strength is high, the water resistance is excellent, and the requirements of class II plywood can be met; the plant protein adhesive has better pre-pressing forming performance even when being glued with a high water content veneer due to the introduction of the modified isocyanate emulsion cross-linking agent, is beneficial to the wood processing process of processing the board, and can be used for producing artificial boards such as plywood, shaving board, medium density fiberboard, joinery board and the like.
The main raw material protein meal is food crop processing residues, is a renewable resource, can solve the problems of recycling of food crop wastes and higher cost of biomass adhesives, solves the problem of excessive dependence of synthetic adhesives on fossil resources, meets the requirements of environmental protection and sustainable development, and has important economic and social benefits.
The method provided by the embodiment of the invention has simple and feasible process and is suitable for industrial production.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The protein meal is defatted soybean meal powder, contains protein more than or equal to 43% (w/w), and has a particle size of 200-250 meshes.
The curing agent used below was glycerol triglycidyl ether (PTGE).
Example 1
The embodiment also provides a preparation method of the modified isocyanate emulsion cross-linking agent, which comprises the following steps:
1. Adding 4kg of tannic acid into 7kg of water, and stirring for 6 minutes by adopting a mechanical stirring method until uniformly mixing to obtain a tannic acid aqueous solution;
2. The prepared aqueous tannic acid solution was added to 20kg of pMDI and emulsified directly for 10 minutes to obtain a uniform modified isocyanate emulsion cross-linking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
The embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 25kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 800 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. 8kg of the modified isocyanate emulsion cross-linking agent of the embodiment is added into the mixed solution containing the protein meal and water under the stirring condition of 900 revolutions per minute, and the mixed solution is stirred for 5 minutes for standby;
3. and (2) adding 6kg of curing agent into the system obtained in the step (2), and stirring for 10 minutes to be uniform at the rotating speed of 900 revolutions per minute to obtain the modified plant protein adhesive.
Example 2
The embodiment provides a modified isocyanate emulsion cross-linking agent which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified isocyanate emulsion cross-linking agent, which comprises the following steps:
1. Adding 3.5kg of tannic acid into 8kg of water, and stirring for 5 minutes by adopting a mechanical stirring method until uniformly mixing to obtain a tannic acid aqueous solution;
2. the prepared aqueous tannic acid solution was added to 20kg of pMDI and emulsified directly for 8 minutes to obtain a homogeneous modified isocyanate emulsion cross-linker.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
The embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. dispersing 28kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. Adding 5kg of the modified isocyanate emulsion cross-linking agent of the embodiment into the mixed solution containing the protein meal and water under the stirring condition of 900 revolutions per minute, and stirring for 6 minutes for later use;
3. and (2) adding 7kg of curing agent into the system obtained in the step (2), and stirring for 15 minutes to be uniform at the rotating speed of 900 revolutions per minute to obtain the modified plant protein adhesive.
Example 3
The embodiment provides a modified isocyanate emulsion cross-linking agent which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified isocyanate emulsion cross-linking agent, which comprises the following steps:
1. adding 5kg of gallic acid into 7kg of water heated to 60 ℃ and stirring for 6 minutes by adopting a mechanical stirring method until the gallic acid is uniformly mixed to obtain a gallic acid aqueous solution;
2. The prepared gallic acid aqueous solution was added to 20kg of pMDI and emulsified directly for 15 minutes to obtain a uniform modified isocyanate emulsion cross-linking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
The embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. Dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. 8kg of the modified isocyanate emulsion cross-linking agent of the embodiment is added into the mixed solution containing the protein meal and water under the stirring condition of 900 revolutions per minute, and the mixed solution is stirred for 5 minutes for standby;
3. and (2) adding 6kg of curing agent into the system obtained in the step (2), and stirring for 12 minutes at the rotating speed of 900 revolutions per minute until the modified plant protein adhesive is obtained uniformly.
Example 4
The embodiment provides a modified isocyanate emulsion cross-linking agent which is prepared from the following raw materials in parts by weight:
the embodiment also provides a preparation method of the modified isocyanate emulsion cross-linking agent, which comprises the following steps:
1. adding 4kg of gallic acid into 6kg of water heated to 60 ℃ and stirring for 5 minutes by adopting a mechanical stirring method until the gallic acid is uniformly mixed to obtain a gallic acid aqueous solution;
2. The prepared gallic acid aqueous solution was added to 20kg of pMDI and emulsified directly for 10 minutes to obtain a uniform modified isocyanate emulsion cross-linking agent.
The embodiment provides a modified vegetable protein adhesive, which is prepared from the following raw materials in parts by weight:
The embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. Dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. 7kg of the modified isocyanate emulsion cross-linking agent of the embodiment is added into the mixed solution containing the protein meal and water under the stirring condition of 900 revolutions per minute, and the mixed solution is stirred for 4 minutes for standby;
3. And (2) adding 8kg of curing agent into the system obtained in the step (2), and stirring for 14 minutes at the rotating speed of 900 revolutions per minute until the modified plant protein adhesive is obtained uniformly.
Comparative example 1 pMDI-modified vegetable protein adhesive alone
The comparative example provides a modified plant protein adhesive which is prepared from the following raw materials in parts by weight:
The embodiment also provides a preparation method of the modified vegetable protein adhesive, which comprises the following steps:
1. Dispersing 30kg of protein meal in 70kg of water, and uniformly stirring at the rotating speed of 900 revolutions per minute to obtain a mixed solution containing the protein meal and the water;
2. 7kg of pMDI (unmodified) was added to the mixed solution containing protein meal and water under stirring at 900 rpm for 5 minutes;
3. and (2) adding 8kg of curing agent into the system obtained in the step (2), and stirring for 14 minutes at the rotating speed of 900 revolutions per minute until the curing agent is uniform to obtain the modified plant protein adhesive.
Experimental example
The following test methods were used:
Solid content test
1. Test materials modified vegetable protein adhesives prepared in examples 1-4 and comparative example 1.
2. The specific test method comprises the following steps:
And (3) placing a proper amount of prepared modified plant protein adhesive m 1 g into a tin foil paper box, recording the total weight of the adhesive and the tin foil paper box m 2 g, then placing the adhesive into a drying oven with the temperature of 122+/-2 ℃ to be dried to constant weight, recording the total weight of the adhesive and the tin foil paper box after curing to be m 3 g, and adopting the calculation formula of the solid content of the adhesive as follows. The above experiments were performed 3 times in parallel and averaged.
The adhesive solid content (W 1) has the following calculation formula:
W1(％)＝[m3-(m2-m1)]/m1×100％
Pre-compaction forming property test
A single board: poplar with water content of 20-30% and thickness of 1.6mm;
Sizing: the core plate is glued, and the gluing amount is 270-325g/m 2 (double-sided);
Cold pressing: the cold pressing pressure is 5-10MPa, and the cold pressing time is 30-60min; ;
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100 s/min)
And (3) after cold pressing is finished according to the conditions, releasing pressure, taking out the plate blank, standing for 30min, observing the condition that the periphery in the vertical direction of the wood fiber is rolled up to be degummed, measuring the side length of the un-glued product, and expressing the pre-pressing molding performance of the glue by the ratio of the side length to the total side length (140 mm). The ratio is less than 40% and 40% -60% are marked as "poor", and more than 60% are marked as "good".
Waterproof glue strength test
The modified protein adhesives prepared in examples 1-4 and comparative example 1 of the present invention were used to prepare three-layer plywood, and the following preparation process parameters were adopted:
a single board: poplar with water content of 20-30% and thickness of 1.6mm;
Sizing: the core plate is glued, and the gluing amount is 270-325g/m 2 (double-sided);
Aging time: 30-90 min;
Hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 MPa; the hot pressing time is 10min (100 s/min)
The three-layer plywood manufactured by the process is tested for the water-resistant bonding strength (class II) according to GB/T17657-2013 artificial board and veneer artificial board physical and chemical property experiment method, and the result is shown in table 1.
TABLE 1 results of testing the main properties of the adhesives of examples 1-4 and comparative example 1 and the plywood prepared
Solid content (%) Pre-press formability Waterproof bonding strength (MPa)
Comparative example 1 37.5 Difficult to form 0.83
Example 1 34.4 Good (good) 1.31
Example 2 34.8 Good (good) 1.27
Example 3 37.2 Preferably, it is 1.34
Example 4 37.6 Good (good) 1.29
The results in Table 1 show that the vegetable protein adhesives added with the isocyanate emulsion crosslinking agents prepared in examples 1-4 have better pre-pressing forming performance than the vegetable protein adhesive in comparative example 1, the water-resistant bonding strength of the adhesives is obviously enhanced, and the requirements of class II plywood are met.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (7)

1. The modified plant protein adhesive is characterized by being prepared from the following raw materials in parts by weight:
70 parts of water, and the water is mixed with the water,
20-40 Parts of protein meal,
2-15 Parts of modified isocyanate emulsion cross-linking agent,
5-10 Parts of curing agent;
The modified isocyanate emulsion cross-linking agent is prepared from the following raw materials in parts by weight: 20 parts of isocyanate, 6-8 parts of water and 3.5-5 parts of modifier; the isocyanate is polydiphenylmethane diisocyanate; the modifier is selected from tannic acid or gallic acid; the preparation method of the modified isocyanate emulsion cross-linking agent comprises the following steps: 1) Providing an aqueous modifier solution; the modifier aqueous solution is prepared from the modifier and water; 2) Mixing the modifier aqueous solution with isocyanate, emulsifying, and polymerizing the modifier with isocyanate;
the curing agent is glycerol triglycidyl ether.
2. The modified vegetable protein adhesive according to claim 1, which is prepared from the following raw materials in parts by weight:
70 parts of water, and the water is mixed with the water,
25-30 Parts of protein meal,
5-8 Parts of modified isocyanate emulsion cross-linking agent,
6-8 Parts of curing agent.
3. The modified vegetable protein adhesive according to claim 1, which is prepared from the following raw materials in parts by weight:
70 parts of water
28-30 Parts of protein meal
6-8 Parts of modified isocyanate emulsion cross-linking agent
7-8 Parts of curing agent.
4. A modified vegetable protein adhesive according to any one of claims 1 to 3, wherein the modified isocyanate emulsion cross-linking agent is prepared from the following raw materials in parts by weight: 20 parts of isocyanate, 6-8 parts of water and 4-5 parts of modifier.
5. The modified plant protein adhesive according to any one of claims 1 to 3, wherein the protein meal is one or more of soybean meal, maple meal, peanut meal, castor meal, cottonseed meal, rapeseed meal, and distillers' grains; and/or the number of the groups of groups,
The granularity of the protein meal is 70-500 meshes; and/or the number of the groups of groups,
The protein meal is defatted protein meal; and/or the number of the groups of groups,
The protein content in the protein meal is more than 40 weight percent.
6. The method for preparing the modified protein adhesive according to any one of claims 1 to 5, comprising the steps of:
a) Providing a mixed solution containing protein meal and water;
b) And mixing the mixed solution containing the protein meal and water with the modified isocyanate emulsion cross-linking agent and the curing agent to prepare the modified plant protein adhesive.
7. Wood, bamboo, furniture, printed matter, construction or finishing trim comprising the modified protein adhesive of any one of claims 1-5.
CN202010066314.7A 2020-01-20 2020-01-20 Modified isocyanate emulsion cross-linking agent, modified adhesive and application Active CN111171256B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010066314.7A CN111171256B (en) 2020-01-20 2020-01-20 Modified isocyanate emulsion cross-linking agent, modified adhesive and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010066314.7A CN111171256B (en) 2020-01-20 2020-01-20 Modified isocyanate emulsion cross-linking agent, modified adhesive and application

Publications (2)

Publication Number Publication Date
CN111171256A CN111171256A (en) 2020-05-19
CN111171256B true CN111171256B (en) 2024-04-19

Family

ID=70652796

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010066314.7A Active CN111171256B (en) 2020-01-20 2020-01-20 Modified isocyanate emulsion cross-linking agent, modified adhesive and application

Country Status (1)

Country Link
CN (1) CN111171256B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112831036A (en) * 2020-12-30 2021-05-25 中国林业科学研究院林业新技术研究所 Plant glycosyl polyester adhesive as well as preparation method and application thereof
CN113308207B (en) * 2021-05-31 2022-10-28 东莞市雄林新材料科技股份有限公司 Water-repellent TPU hot melt adhesive film and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02202573A (en) * 1989-01-31 1990-08-10 Nippon Oil & Fats Co Ltd Adhesive composition
EP0526815A1 (en) * 1991-08-06 1993-02-10 Bayer Ag Process for tanning/impregnation and/or post-tanning of leather
CN107840939A (en) * 2017-11-17 2018-03-27 陕西环珂生物科技有限公司 The preparation method of tannic acid modified aqueous polyurethane
CN109575878A (en) * 2018-11-09 2019-04-05 中国林业科学研究院林产化学工业研究所 One kind being based on dregs of beans adhesive tannin based cross-linker and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02202573A (en) * 1989-01-31 1990-08-10 Nippon Oil & Fats Co Ltd Adhesive composition
EP0526815A1 (en) * 1991-08-06 1993-02-10 Bayer Ag Process for tanning/impregnation and/or post-tanning of leather
CN107840939A (en) * 2017-11-17 2018-03-27 陕西环珂生物科技有限公司 The preparation method of tannic acid modified aqueous polyurethane
CN109575878A (en) * 2018-11-09 2019-04-05 中国林业科学研究院林产化学工业研究所 One kind being based on dregs of beans adhesive tannin based cross-linker and its application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Designing Biomimetic Microphase-Separated Motifs to Construct Mechanically Robust Plant Protein Resin with Improved Water-Resistant Performance;Zhao Shunjun;Macromolecular Materials and Engineering》;第305卷;第1900462页 *
李绍雄.《聚氨酯树脂及其应用》.化学工业出版社,2002,第19-20页. *

Also Published As

Publication number Publication date
CN111171256A (en) 2020-05-19

Similar Documents

Publication Publication Date Title
CN111171314B (en) Modified PAE resin crosslinking agent, modified adhesive and application
CN111171256B (en) Modified isocyanate emulsion cross-linking agent, modified adhesive and application
CN110272715B (en) High-temperature peanut meal-based formaldehyde-free adhesive and preparation method and application thereof
CN111171783B (en) Modified wood fiber reinforced plant protein adhesive and preparation method and application thereof
CN103740324B (en) A kind of adhesion agent for artificial board and its preparation method and application
CN105583935B (en) A kind of method that environment protecting fiber board is prepared based on chitosan blend lignin
CN111171277B (en) Polyurethane elastic crosslinking agent, high-strength and high-toughness vegetable protein adhesive and application
CN111234132B (en) Water-based epoxy resin cross-linking agent, modified protein adhesive and application
CN112831036A (en) Plant glycosyl polyester adhesive as well as preparation method and application thereof
CN105907119A (en) Formaldehyde-free medium-density fiber board and manufacturing method thereof
CN109536126A (en) A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application
CN108943308A (en) A kind of environment-protective adhesive and preparation method thereof can be used for beaver board
CN114134751A (en) Novel waterproof composite resin for impregnating surface layer of laminate wood floor and preparation method thereof
CN107033832B (en) Formaldehyde-free composite adhesive for artificial board and preparation method thereof
CN112322243B (en) Waterproof polyamide-based adhesive and preparation method thereof
CN111040663B (en) Soybean-based protein adhesive for artificial board and preparation method thereof
CN104212123B (en) A kind of compound alkalescent phenol resin firming agent, preparation method and application
CN103740325B (en) Adhesion agent for artificial board, its preparation method and utilize its glued board
CN103320081B (en) High-molecular composite adhesive, and preparation method and application thereof
CN109401726B (en) PEI-g-HBA prepolymer vegetable protein composite modified adhesive as well as preparation method and application thereof
CN114108365A (en) Melamine softening coated paper and production process thereof
CN106753221A (en) A kind of modified vegetable protein adhesive and preparation method and application
CN110964434B (en) Aldehyde-free green environment-friendly adhesive and preparation method thereof
CN106182327A (en) A kind of zero formaldehyde bamboo shaving plate and preparation method thereof
CN106800913A (en) A kind of modified timber-used soy protein adhesives and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant