CN112300756A - Modified nano-cellulose reinforced soy protein adhesive and preparation method thereof - Google Patents
Modified nano-cellulose reinforced soy protein adhesive and preparation method thereof Download PDFInfo
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B3/12—Preparation of cellulose esters of organic acids of polybasic organic acids
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/14—Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl
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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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/10—Esters of organic acids
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Abstract
The invention discloses a modified nano-cellulose reinforced soy protein adhesive which is prepared from the following raw materials in parts by mass: 20-40% of soybean protein, 1-5% of butane tetracarboxylic acid, 0.5-3% of sodium hypophosphite, 30-70% of nano cellulose aqueous solution and 2-10% of a grafting agent; the grafting agent contains an epoxy group. The preparation method comprises the following steps: (1) adding 1,2,3, 4-butanetetracarboxylic acid and sodium hypophosphite into a nano-cellulose aqueous solution to obtain esterified nano-cellulose containing carboxyl; (2) adding a grafting agent into the obtained reactant (1) to obtain epoxy-containing nanocellulose; (3) adding the soybean protein into the reaction product (2), and reacting at room temperature for 1-2h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The modified nano-cellulose reinforced soy protein adhesive is environment-friendly, green, nontoxic and excellent in performance, and does not have the problem of formaldehyde release when being used for an artificial board adhesive.
Description
Technical Field
The invention relates to a modified nano-cellulose reinforced soy protein adhesive and a preparation method thereof, belonging to the field of wood adhesives.
Background
The yield of the adhesive for the wood industry accounts for about 75% of the total global adhesive yield, and the adhesive is the largest adhesive product. With the rapid development of the wood industry, the consumption of wood adhesives is continuously increased, and the manufacturing level of the adhesives becomes an important mark for measuring the development level of the wood industry in a country or a region. In recent years, with the rapid development of artificial boards, interior decoration and furniture industries in China, the using amount of wood adhesives is greatly increased, and China becomes a large country for wood adhesive production. However, wood adhesives in China still take 'three-aldehyde glue' (urea-formaldehyde resin, phenolic resin and melamine formaldehyde resin) as the leading factor, and the 'three-aldehyde glue' and products thereof can release harmful substances such as formaldehyde and the like in the production and use processes, so that air pollution is caused, and human health is harmed. With the improvement of the requirements of people on living environment and the development of novel structural boards, the novel wood adhesive with ultra-low formaldehyde release, non-aldehyde series, biomass base and other high performance, environmental protection and low carbon has become an important development direction of the current wood adhesive industry.
The soybean protein is a non-toxic natural high polymer material, and since the last 90 years, a series of research works on soybean protein adhesives have been carried out at home and abroad, wherein the industrial production of part of modified soybean protein adhesives has been realized. Because a large number of polar and nonpolar groups exist in natural soybean protein molecules, a stable multilevel structure is formed through hydrogen bonds, van der waals force and the like, and the adhesion effect of the soybean protein is poor, certain modification is needed to expose more polar and nonpolar groups, so that the soybean protein has an adsorption effect with wood, and the adhesion strength is improved. At present, the modification of the soybean protein adhesive in China mostly adopts a resin copolymerization or blending method, so that the soybean protein adhesive still has volatile toxic compounds, and the development aim of environmental protection is violated. The nanocellulose as a biomass material has good degradability, and meanwhile, because a large number of hydroxyl groups exist on the surface of the nanocellulose, on one hand, the nanocellulose can be subjected to esterification reaction with acid to introduce a large number of groups such as carboxyl groups, amino groups and the like with reaction activity, and after epoxidation, the groups can be subjected to cross-linking polymerization reaction with active groups in the soybean protein to enhance the water-resistant bonding performance of the nanocellulose; on the other hand, the dispersibility and the hydrophobicity of the whole reaction system can be improved by modification.
Disclosure of Invention
The invention aims to provide an environment-friendly, non-toxic and excellent-performance modified nano-cellulose reinforced soybean protein adhesive and a preparation method thereof.
The technical scheme adopted by the invention is as follows: the modified nano-cellulose reinforced soy protein adhesive is prepared from the following raw materials in parts by mass: 20-40% of soybean protein, 1-5% of butane tetracarboxylic acid, 0.5-3% of sodium hypophosphite, 30-70% of nano cellulose aqueous solution and 2-10% of a grafting agent; the grafting agent contains an epoxy group.
The grafting agent is epichlorohydrin and/or glycidyl ether, and the epoxy group in the glycidyl ether is more than or equal to 2.
The glycidyl ether is ethylene glycol diglycidyl ether, bisphenol A dianhydro-glycidyl ether, pentaerythritol glycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether or trimethylolpropane triglycidyl ether.
The soybean protein is defatted soybean powder, defatted soybean meal and soybean protein isolate, and is pulverized into powder with a particle size of not less than 200 meshes and a fat content of less than 5%.
The preparation method of the modified nano-cellulose reinforced soy protein adhesive comprises the following steps:
(1) adding 1,2,3, 4-butanetetracarboxylic acid and sodium hypophosphite into a nano cellulose aqueous solution, and stirring for 1-3h in a water bath at 40-60 ℃ to obtain esterified nano cellulose containing carboxyl;
(2) adding a grafting agent into the obtained reactant (1), adjusting the pH value to 8-10, and carrying out heat preservation reaction at 35 ℃ for 1-3h to obtain epoxy-containing nanocellulose;
(3) adding the soybean protein into the reaction product (2), and reacting at room temperature for 1-2h to obtain the modified nano-cellulose reinforced soybean protein adhesive.
The reagent used for adjusting the pH value in the step (2) is one or a mixture of more of sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate, and preferably sodium hydroxide and potassium hydroxide.
Compared with the prior art, the invention has the following advantages:
1) the modified nano-cellulose reinforced soybean protein adhesive disclosed by the invention is prepared from environment-friendly materials, is non-toxic and is easy to degrade; the nano-cellulose aqueous solution (with the concentration of 2-3%) is purchased from the institute of Wood industry of China institute of forestry science.
2) Firstly, carrying out esterification reaction on nano-cellulose to introduce carboxyl with reaction activity into nano-cellulose molecules, improving the reaction activity of the nano-cellulose, and then using an epoxy compound as a grafting agent to carry out addition reaction with the carboxyl on the nano-cellulose to generate modified nano-cellulose containing a large number of epoxy groups; and then, adding the soybean protein to perform a cross-linking polymerization reaction on amino and hydroxyl on the soybean protein molecule and an epoxy group on the modified nanocellulose to generate a soybean protein adhesive system with a water-resistant network structure.
3) The chemical reagent adopted by the invention for grafting modification of the nano-cellulose does not contain formaldehyde, and the prepared soybean protein does not have the problem of formaldehyde release when being used for an artificial board adhesive.
4) The nano-cellulose used in the invention has wide raw material sources and comprises lignocellulose, herbaceous plant cellulose and bamboo cellulose.
Detailed Description
The invention is further defined in the following by reference to specific embodiments:
example 1
30% of defatted soybean powder, 5% of butane tetracarboxylic acid, 3% of sodium hypophosphite, 55% of nano cellulose aqueous solution and 7% of ethylene glycol diglycidyl ether.
(1) 50 kg of 1,2,3, 4-butanetetracarboxylic acid and 30 kg of sodium hypophosphite are added into 550 kg of nano-cellulose aqueous solution in a reaction kettle, and stirred for 1h in a water bath at the temperature of 60 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 70 kg of ethylene glycol diglycidyl ether into the obtained reactant (1), adjusting the pH value to 10, and carrying out heat preservation reaction at 35 ℃ for 2.5h to obtain the epoxy group-containing nanocellulose.
(3) And (3) adding 300 kg of defatted soybean flour into the reaction product (2), and reacting at room temperature for 1.5h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 2
20% of degreased soybean meal, 3% of butane tetracarboxylic acid, 2% of sodium hypophosphite, 70% of nano cellulose aqueous solution and 5% of pentaerythritol glycidyl ether.
(1) 30 kg of 1,2,3, 4-butanetetracarboxylic acid and 20 kg of sodium hypophosphite are added into 700 kg of nano-cellulose aqueous solution in a reaction kettle, and the mixture is stirred for 3 hours in a water bath at the temperature of 40 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 50 kg of pentaerythritol glycidyl ether into the obtained reactant (1), adjusting the pH value to 9, and reacting for 3 hours at the temperature of 35 ℃ to obtain the epoxy-containing nanocellulose.
(3) And (3) adding 200 kg of defatted soybean meal into the reaction product (2), and reacting at room temperature for 2h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 3
40% of soybean protein isolate, 1% of butane tetracarboxylic acid, 0.5% of sodium hypophosphite, 55% of nano cellulose aqueous solution and 3.5% of diethylene glycol diglycidyl ether.
(1) 10 kg of 1,2,3, 4-butanetetracarboxylic acid and 5 kg of sodium hypophosphite are added into 550 kg of nano-cellulose aqueous solution in a reaction kettle, and stirred for 1.5h in a water bath at 50 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 35 kg of diethylene glycol diglycidyl ether into the obtained reactant (1), adjusting the pH value to 10, and carrying out heat preservation reaction at 35 ℃ for 2.5h to obtain the epoxy group-containing nanocellulose.
(3) Adding 400 kg of soybean protein isolate into the reaction product (2), and reacting at room temperature for 1.5h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 4
25% of degreased bean flour, 2.5% of butane tetracarboxylic acid, 1.5% of sodium hypophosphite, 66% of nano cellulose aqueous solution and 5% of trimethylolpropane triglycidyl ether.
(1) Adding 25 kg of 1,2,3, 4-butanetetracarboxylic acid and 15 kg of sodium hypophosphite into 660 kg of nano-cellulose aqueous solution in a reaction kettle, and stirring for 1h in a water bath at 55 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 50 kg of trimethylolpropane triglycidyl ether into the obtained reactant (1), adjusting the pH value to 8.5, and reacting for 3 hours at the temperature of 35 ℃ to obtain the epoxy-containing nanocellulose.
(3) Adding 250 kg of defatted soybean flour into the reaction product (2), and reacting at room temperature for 2.5h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 5
30% of soybean protein isolate, 3% of butane tetracarboxylic acid, 1% of sodium hypophosphite, 60% of nano-cellulose aqueous solution, 4% of ethylene glycol diglycidyl ether and 2% of trimethylolpropane triglycidyl ether.
(1) 30 kg of 1,2,3, 4-butanetetracarboxylic acid and 10 kg of sodium hypophosphite are added into 600 kg of nano-cellulose aqueous solution in a reaction kettle, and stirred for 3h in a water bath at the temperature of 45 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 40 kg of ethylene glycol diglycidyl ether and 20 kg of trimethylolpropane triglycidyl ether into the obtained reactant (1), adjusting the pH value to 9.5, and carrying out heat preservation reaction at 35 ℃ for 2.5h to obtain the epoxy group-containing nanocellulose.
(3) Adding 300 kg of soybean protein isolate into the reaction product (2), and reacting at room temperature for 1.5h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 6
25% of defatted soybean powder, 4% of butane tetracarboxylic acid, 2% of sodium hypophosphite, 60% of nano-cellulose aqueous solution, 5% of diethylene glycol diglycidyl ether and 4% of bisphenol A diglycidyl ether.
(1) 40 kg of 1,2,3, 4-butanetetracarboxylic acid and 20 kg of sodium hypophosphite are added into 600 kg of nano-cellulose aqueous solution in a reaction kettle, and stirred for 1h in a water bath at 50 ℃ to obtain the esterified nano-cellulose containing carboxyl.
(2) Adding 50 kg of diethylene glycol diglycidyl ether and 40 kg of bisphenol A dianhydro-glycidyl ether into the obtained reactant (1), adjusting the pH value to 9, and carrying out heat preservation reaction at 35 ℃ for 3h to obtain the epoxy-containing nanocellulose.
(3) Adding 250 kg of defatted soybean flour into the reaction product (2), and reacting at room temperature for 1h to obtain the modified nano-cellulose reinforced soybean protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Comparative example 1
The modified nanocellulose-reinforced soy protein adhesive was prepared in the same manner as in example 1. The difference is that butane tetracarboxylic acid is not added in the step 1 to carry out esterification reaction, and the soybean protein adhesive is directly prepared. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Comparative example 2
A vegetable protein adhesive was prepared in the same manner as in example 1. Except that no graft (ethylene glycol diglycidyl ether) is added in the step 2 to directly prepare the soy protein adhesive. The main technical indexes of the obtained modified nano-cellulose reinforced soy protein adhesive are shown in table 1.
Example 7
In order to verify the performance and the application effect of the soybean protein adhesive on a plywood product and the advantages of environmental protection and no harm to human bodies, the invention develops a series of tests, and the specific contents are as follows:
the adhesives prepared in the above examples 1 to 6 and comparative examples 1 to 2 were subjected to performance tests such as shelf life, viscosity, free formaldehyde, free benzene compounds (benzene, toluene, xylene) and the like, and the application effect of the soybean protein adhesive on plywood products was evaluated by preparing 5-layer poplar plywood and detecting the bonding strength and formaldehyde emission thereof. Wherein, the tests of the storage period, the viscosity and the free formaldehyde are carried out according to corresponding detection methods specified in GB/T14074-.
The veneers used for preparing the 7-layer plywood are 6-year fast-growing poplar veneers (600 mm in length, 600 mm in width and 3.0 mm in thickness), and the water content is 10-15%; the preparation process parameters of the 5-layer plywood are as follows: (1) sizing: double-sided sizing with the sizing amount of 380-400/m2(ii) a (2) Aging mode and time: closing and aging for 30 min; (3) a prepressing mode: cold pressing for 30min under 0.7 MPa; (4) hot pressing parameters: the pressure is 0.9Mpa, the temperature is 120 ℃, and the hot pressing time is 17 minutes.
The bonding strength and formaldehyde emission of 5-layer plywood prepared by the vegetable protein adhesive obtained by 6 examples and the adhesive obtained by 2 comparative examples were tested according to the bonding strength test method of type II plywood and the dryer method in formaldehyde emission measurement specified in GB/T17657-2013 physicochemical property test method of artificial board and veneer artificial board, and the results are shown in Table 2.
TABLE 1 Performance parameters of the soy protein adhesives obtained in examples 1-6 and comparative examples 1-2
As can be seen from table 1, the raw materials of the protein adhesive mainly come from regenerated soy protein, nanocellulose, non-aldehyde substances and non-benzene compounds, so that the vegetable protein adhesive prepared by the methods of embodiments 1 to 6 and the methods of comparative examples 1 to 2 does not contain toxic and harmful substances such as free formaldehyde, free benzene compounds and the like, and the green environmental protection of the adhesive is ensured.
The viscosity of the soybean protein adhesive prepared by the methods of the embodiments 1 to 6 is 6694 to 10019mPa.s, while the viscosity of the adhesive prepared by the methods of the comparative examples 1 to 2 is lower, so that the initial viscosity and the bonding performance of the adhesive are influenced.
The shelf life of the soybean protein adhesive prepared by the methods of the embodiments 1 to 6 is 8 hours after glue mixing, and the requirement that the protein adhesive is applied to plywood production for at least more than 4 hours is met.
TABLE 2 Performance parameters of adhesive-bonded plywood obtained in examples 1 to 6 and comparative examples 1 to 2
As shown in table 2, the plywood prepared by using the soy protein adhesive prepared by the methods of embodiments 1 to 6 of the present invention has high bonding strength, and meets the bonding strength (not less than 0.70 MPa) of the type ii plywood specified in the national standard GB/T17657-2013 "test method for physical and chemical properties of artificial boards and veneers), while the resin adhesive prepared by using the comparative example method lacks a certain experimental link in esterification of nanocellulose and graft modification of epoxy groups because the method is not performed according to the method and the steps involved in the present invention, so that the bonding strength of the plywood prepared by using the comparative example method is less than 0.70MPa, and does not reach the national standard of the type ii plywood.
The plywood manufactured by the soybean protein adhesive prepared by the methods of the embodiments 1 to 6 of the invention has extremely low trace formaldehyde release, which is caused by the fact that wood can release formaldehyde, and the formaldehyde release value of the poplar veneer is about 0.04 to 0.08mg/L, which shows that the manufactured plywood has no other aldehydes, toxic and harmful substances except the ultralow formaldehyde released by the wood. The embodiments of the present invention are not only described for the preferred embodiments of the present invention, but also for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical content of the present invention as claimed is fully described in the claims.
Claims (6)
1. The modified nano-cellulose reinforced soy protein adhesive is prepared from the following raw materials in parts by mass: 20-40% of soybean protein, 1-5% of butane tetracarboxylic acid, 0.5-3% of sodium hypophosphite, 30-70% of nano cellulose aqueous solution and 2-10% of a grafting agent; the grafting agent contains an epoxy group.
2. The modified nanocellulose-reinforced soy protein adhesive as claimed in claim 1, wherein the grafting agent is epichlorohydrin and/or glycidyl ether, and epoxy group in the glycidyl ether is not less than 2.
3. The modified nanocellulose-reinforced soy protein adhesive of claim 2, wherein said glycidyl ether is ethylene glycol diglycidyl ether, bisphenol a diglycidyl ether, pentaerythritol glycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, or trimethylolpropane triglycidyl ether.
4. The modified nanocellulose-enhanced soybean protein adhesive as claimed in claim 1, wherein the soybean protein is defatted soybean flour, defatted soybean meal or soybean protein isolate, and is processed into powder by crushing, wherein the particle size is not less than 200 meshes, and the oil content is less than 5%.
5. The preparation method of the modified nanocellulose-reinforced soy protein adhesive according to any one of claims 1 to 4, comprising the following steps:
(1) adding 1,2,3, 4-butanetetracarboxylic acid and sodium hypophosphite into a nano cellulose aqueous solution, and stirring for 1-3h in a water bath at 40-60 ℃ to obtain esterified nano cellulose containing carboxyl;
(2) adding a grafting agent into the obtained reactant (1), adjusting the pH value to 8-10, and carrying out heat preservation reaction at 35 ℃ for 1-3h to obtain epoxy-containing nanocellulose;
(3) adding the soybean protein into the reaction product (2), and reacting at room temperature for 1-2h to obtain the modified nano-cellulose reinforced soybean protein adhesive.
6. The preparation method of the modified nanocellulose-reinforced soy protein adhesive according to claim 5, wherein the preparation method comprises the following steps: the reagent for adjusting the pH value is one or a mixture of more of sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate.
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| CN113583601A (en) * | 2021-08-30 | 2021-11-02 | 广西完美木业集团有限公司 | Waterproof and anticorrosive surface glue for plywood and preparation method thereof |
| CN115781844A (en) * | 2022-12-05 | 2023-03-14 | 德华兔宝宝装饰新材股份有限公司 | Preparation method of high-color-fastness nano modified decorative veneer |
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