CN113292962A - Castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive and preparation method thereof - Google Patents
Castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive and preparation method thereof Download PDFInfo
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- CN113292962A CN113292962A CN202110674659.5A CN202110674659A CN113292962A CN 113292962 A CN113292962 A CN 113292962A CN 202110674659 A CN202110674659 A CN 202110674659A CN 113292962 A CN113292962 A CN 113292962A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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Abstract
The invention discloses a castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive and a preparation method thereof, which solve the problem of poor water resistance of a gelatin-based adhesive for plywood. The method specifically comprises the following steps: castor oil, isophorone diisocyanate and 2, 2-dimethylolbutyric acid are used as main raw materials to prepare castor oil-based waterborne polyurethane; compounding urea and sodium dodecyl sulfate with modified gelatin to prepare gelatin liquefact with high solid content; uniformly spraying an alkali solution into the fenugreek gum, uniformly mixing, drying, cooling and crushing to obtain fenugreek gum powder subjected to alkali heat treatment; mixing the prepared castor oil-based waterborne polyurethane, the gelatin liquefaction product, the polyamide epichlorohydrin and the alkali heat-treated fenugreek gum powder according to a certain proportion to prepare the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive. The invention effectively improves the water resistance and the bonding strength of the adhesive, and the prepared adhesive has good bonding strength and water resistance.
Description
Technical Field
The invention belongs to the field of wood adhesives, and particularly relates to a preparation method of a biomass-based adhesive for plywood.
Background
The wood adhesive is a substance which must be used in the manufacturing process of the artificial board, and the annual demand is huge, but the wood adhesive used at present mainly comprises formaldehyde-based adhesive, and has the problems of poor environmental protection, non-renewable raw materials and the like. Therefore, the development of biomass-based formaldehyde-free environment-friendly adhesives is receiving more and more attention.
Gelatin is a renewable natural polymer material with abundant resources, can be derived from animal skin, bone, etc., and contains amino (-NH) in its molecular structure2) And hydrophilic active groups such as hydroxyl (-OH), carboxyl (-COOH) and the like, and the existence of the polar groups enables the polar groups to form physical adsorption such as hydrogen bonds and the like with the wood matrix, so that the gelatin-based adhesive is endowed with good dry adhesive strength, and the gelatin-based adhesive has the defect of poor water resistance. The fenugreek gum is a biomass resource with rich resources, contains rich active hydroxyl in a molecular structure, is developed and utilized less at present, and has good tackifying and crosslinking characteristics. The single castor oil-based waterborne polyurethane used as the adhesive has the disadvantages of unsatisfactory water resistance and high cost.
Disclosure of Invention
Because the castor oil-based waterborne polyurethane, the gelatin liquefied product and the alkali-heat treated fenugreek gum are derived from renewable biomass resources and the polyamide polyamine epichlorohydrin has high crosslinking efficiency on the gelatin liquefied product, the development of the castor oil-based waterborne polyurethane/gelatin adhesive with excellent water resistance has important significance for enriching formaldehyde-free environment-friendly adhesive products and expanding the application field of the castor oil-based waterborne polyurethane/gelatin adhesive. The invention aims to provide a castor oil-based waterborne polyurethane/gelatin adhesive with excellent water resistance and a preparation method thereof, and solves the problem that the water resistance of the gelatin-based adhesive and the castor oil-based waterborne polyurethane is not ideal.
The specific technical scheme of the invention is as follows:
a preparation method of a castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive comprises the following steps:
castor oil and isophorone diisocyanate form a polyurethane prepolymer, and then castor oil-based waterborne polyurethane is obtained through chain extension of a hydrophilic monomer 2, 2-dimethylolbutyric acid, neutralization of triethylamine and water dispersion; modifying gelatin by urea and sodium dodecyl sulfate to obtain gelatin liquefact with high solid content and low viscosity; uniformly spraying an alkali solution into the fenugreek gum, uniformly mixing, drying, cooling and crushing to obtain fenugreek gum powder subjected to alkali heat treatment; uniformly mixing and stirring the castor oil-based waterborne polyurethane, the gelatin liquefied product, the polyamide epichlorohydrin and the alkali-heat-treated fenugreek gum powder at normal temperature to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
The castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive is prepared by the following steps:
1) according to the mass parts, firstly, fully stirring and mixing 100-300 parts of gelatin liquefied material and 15-60 parts of cross-linking agent polyamide epichlorohydrin;
2) adding 100 portions of castor oil water polyurethane and 300 portions, fully stirring and mixing;
3) finally, 20-100 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive.
The solid content of the castor oil-based waterborne polyurethane is 30-36%; the solid content of the gelatin liquefact is 35-60%; the mass fraction of the alkali solution is 30-50%; the solid content of the polyamide epichlorohydrin is 12.5-20%.
The castor oil-based waterborne polyurethane is obtained by a method comprising the following steps:
1) according to the mass percent, adding 170 parts of castor oil, 120-170 parts of isophorone diisocyanate, 150 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate into a reaction kettle, reacting at the temperature of 60-70 ℃ and the rotating speed of 200-400rpm for 2.5-3.5 h;
2) slowly adding 30-55 parts of triethylamine into the reaction kettle, and stirring for 0.5-1 h;
3) adding 900 parts of 500-1200 rpm water for dispersion, adjusting the rotation speed to 1000-1200rpm, and stirring for 0.5-1h to obtain the castor oil-based waterborne polyurethane.
The gelatin liquefact is obtained by the method comprising the following steps:
1) adding 100 parts of water, 5-8 parts of urea and 2-4 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving, and heating to 75-80 ℃;
2) and then slowly adding 55-150 parts of gelatin (the gelatin is added within 15 minutes), stirring for 1-1.5 hours until the gelatin is completely dissolved, and finally cooling the product to room temperature to obtain a gelatin liquefied product.
The alkali-heat treated fenugreek gum powder is obtained by a method comprising the following steps:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 2-6 parts of an alkali solution, and uniformly mixing;
2) drying the product obtained in the step 1 in an oven at the temperature of 90-120 ℃ for 60-180 min;
3) and (3) drying the product obtained in the step (2) at 65 ℃ until the water content is 6-9%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
The alkali solution in the step 2 is sodium hydroxide or potassium hydroxide solution.
The method specifically comprises the following steps:
step one, preparing castor oil-based waterborne polyurethane:
1) according to the mass percent, adding 170 parts of castor oil, 120-170 parts of isophorone diisocyanate, 150 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate into a reaction kettle, reacting at the temperature of 60-70 ℃ and the rotating speed of 200-400rpm for 2.5-3.5 h;
2) slowly adding 30-55 parts of triethylamine into the reaction kettle, and stirring for 0.5-1 h;
3) adding 900 parts of 500-1200 rpm water for dispersion, adjusting the rotation speed to 1000-1200rpm, and stirring for 0.5-1h to obtain the castor oil-based waterborne polyurethane with the solid content of 30-36%;
step two, preparing a gelatin liquefaction product:
1) adding 100 parts of water, 5-8 parts of urea and 2-4 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving, and heating to 75-80 ℃;
2) then slowly adding 55-150 parts of gelatin (the gelatin is added within 15 minutes) into the reaction kettle, stirring for 1-1.5 hours until the gelatin is completely dissolved, and finally cooling the product to room temperature to obtain a gelatin liquefaction product with the solid content of 35-60%;
step three, preparing the fenugreek gum powder subjected to alkali heat treatment:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 2-6 parts of sodium hydroxide or potassium hydroxide solution (the mass fraction is 30% -50%), and uniformly mixing;
2) drying the product obtained in the step one in an oven at the temperature of 90-120 ℃ for 60-180 min;
3) drying the product obtained in the second step at 65 ℃ until the water content is 6-9%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder;
step four, preparing the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive:
1) according to the mass parts, firstly, fully stirring and mixing 100-300 parts of gelatin liquefied material and 15-60 parts of cross-linking agent polyamide epichlorohydrin (the solid content is 12.5% -20%);
2) adding 100 parts of castor oil-based waterborne polyurethane and 300 parts of castor oil-based waterborne polyurethane, and fully stirring and mixing;
3) finally, 20-100 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
The castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive is prepared by the preparation method.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the raw materials of castor oil, gelatin and fenugreek gum used in the invention have the characteristics of abundant resources, renewability, environmental protection and the like, and are beneficial to realizing industrial application. Toxic solvents are not used in the preparation process, the preparation method is simple, and the raw materials are easy to obtain.
(2) The invention provides a preparation method of a castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive, wherein a method of blending castor oil-based waterborne polyurethane, gelatin liquefied product, alkali-heat treated fenugreek gum powder and a cross-linking agent polyamide polyamine epoxy chloropropane is adopted in the preparation process, so that the cross-linking curing condition is mild, the process is simple, the repeatability is good, and the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive has popularization and application potentials.
(3) According to the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive prepared by the invention, the water resistance and the bonding strength of the adhesive are effectively improved by adjusting the solid contents of the castor oil-based waterborne polyurethane and the gelatin liquefied product, introducing alkali-heat treated fenugreek gum powder and regulating and controlling the proportion of the castor oil-based waterborne polyurethane, the gelatin liquefied product and the cross-linking agent polyamide epichlorohydrin, and the adhesive has good bonding strength and water resistance to a plywood prepared from birch.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative of the present invention and are not to be construed as limiting the scope of the invention, but also include any combination of the individual embodiments. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.
Example 1
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 20 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 100 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 20 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Example 2
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 30 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 100 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 20 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Example 3
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 40 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 100 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 20 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Example 4
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 20 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 100 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 30 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Example 5
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 20 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 100 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 40 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Example 6
The method comprises the following steps: preparation of castor oil-based waterborne polyurethane
1) According to the mass ratio, 150 parts of castor oil, 150 parts of isophorone diisocyanate, 40 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate are added into a reaction kettle, and the reaction is carried out at the temperature of 60 ℃ and the rotating speed of 250rpm for 3.5 h.
2) 40 parts of triethylamine is slowly added into the reaction kettle and stirred for 1 hour.
3) Adding 700 parts of water for dispersion, adjusting the rotating speed to 1000rpm, and stirring for 1h to obtain the castor oil-based waterborne polyurethane.
Step two: preparation of gelatin liquefact:
1) adding 100 parts of water, 5 parts of urea and 2 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving and heating to 75 ℃;
2) and slowly adding 100 parts of gelatin into the reaction kettle, stirring for 1 hour to fully dissolve the gelatin, and cooling the product to room temperature to obtain a gelatin liquefied product.
Step three: preparation of alkali-heat treated fenugreek gum powder:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 4 parts of 50% sodium hydroxide solution by mass, and uniformly mixing;
2) drying the product obtained in the step one in an oven at 110 ℃ for 120 min;
3) and (3) drying the product obtained in the step two at 65 ℃ until the water content is 8%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
Step four: preparation of castor oil based waterborne polyurethane/gelatin interpenetrating network polymer adhesive
1) According to the mass parts, 100 parts of gelatin liquefaction product and 20 parts of cross-linking agent polyamide epichlorohydrin are fully stirred and mixed;
2) adding 200 parts of castor oil water polyurethane, and fully stirring and mixing;
3) finally, 20 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
Comparative example 1
Compared with the example 1, the comparative example is different only in that the castor oil-based waterborne polyurethane in the first step and the fourth step is removed, and the rest of the raw materials and the process are the same as those in the example 1.
Comparative example 2
This comparative example is different from example 1 only in that the alkali-heat treated fenugreek gum powder in step three and step four was removed, and the remaining raw materials and processes were the same as those of example 1.
Comparative example 3
Compared with the example 1, the comparative example is different only in that the polyamide epichlorohydrin in the step four is removed, and the rest of the raw materials and the process are the same as those in the example 1.
Comparative example 4
Compared with the example 1, the comparative example is different only in that the gelatin liquefied product and the polyamide epichlorohydrin in the second step and the fourth step are removed, and the rest of the raw materials and the process are the same as those in the example 1.
Comparative example 5
Compared with the example 1, the comparative example is different only in that urea and sodium dodecyl sulfate used for dissolving gelatin in the step two are removed, the gelatin is directly dissolved by hot water, and the rest raw materials and processes are the same as those in the example 1.
Comparative example 6
Compared with the example 1, the difference of the comparative example is that the fenugreek gum powder in the third step is not subjected to alkali heat treatment, the crushed fenugreek gum powder is directly used, and the rest of the raw materials and the process are the same as those in the example 1.
The adhesives prepared in all the examples and the comparative examples are used for bonding birch veneers to prepare three-layer plywood, and the mechanical property and the water resistance of the plywood are tested as follows: the results are shown in Table 1.
Attached table 1
Note: dry strength is the strength measured directly in the dry state; the wet strength is the strength after soaking in water at 63 ℃ for 4 h; the boiling strength is the strength after boiling in boiling water for 4 h. NA indicates that the sample was destroyed.
In the first step of the invention, the castor oil molecule structure contains active hydroxyl which can react with an isocyanate group (-NCO) in isophorone diisocyanate, a hydrophilic monomer 2, 2-dimethylolbutyric acid is introduced to improve the molecular weight of the polyurethane prepolymer, triethylamine and carboxyl in a reaction system are utilized to form salt through neutralization reaction, and water is used as a dispersant to be stirred at high speed to obtain the castor oil-based waterborne polyurethane.
The invention has two stepsThe purpose of the liquefaction treatment of the gelatin is to loosen the structure of the gelatin and prepare a gelatin liquefaction product with high solid content and low viscosity. The invention uses urea to destroy the hydrogen bond force between gelatin molecules, uses sodium dodecyl sulfate to destroy the hydrophobic force between gelatin molecules, and uses high temperature condition and these modifying agents to loosen the gelatin structure and make the active group (-NH) in the gelatin molecular structure2OH, -COOH) are released sufficiently.
One of the purposes of the present invention, step three, in preparing the alkali-heat treated fenugreek gum powder, is to adjust the viscosity of the gelatin-based adhesive system so that it has good sizing properties. When the viscosity is too low, the adhesive is easy to permeate into the porous structure of the wood, so that the adhesive bonding layer is in adhesive shortage, and when the viscosity of the adhesive is too high, the adhesive is difficult to be uniformly coated on the wood substrate, so that the adhesive is not uniformly applied; the other purpose is that the alkali-heat treated fenugreek gum powder can be used as an active filler, has a tackifying effect and is beneficial to improving the water resistance of the adhesive.
According to the invention, active groups (amino, hydroxyl and carboxyl) of gelatin and nitrogen heterocyclic structures in polyamide polyamine epoxy chloropropane can form a firm three-dimensional cross-linked network structure through chemical cross-linking, castor oil-based waterborne polyurethane can form a three-dimensional network structure through self cross-linking, and the two network structures are interpenetrated, wound and interpenetrated, so that the water resistance of an adhesive system is enhanced. In addition, the fenugreek gum introduced with alkali-heat treatment endows an adhesive system with ideal viscosity on one hand, and can be used as an active filler on the other hand, so that the water resistance of the adhesive is improved. The castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive with excellent water resistance can be obtained by regulating and controlling the proportion of the gelatin liquefact, the aqueous polyurethane, the polyamide epichlorohydrin and the alkali heat-treated fenugreek gum.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive is characterized by comprising the following steps:
castor oil and isophorone diisocyanate form a polyurethane prepolymer, and then castor oil-based waterborne polyurethane is obtained through chain extension of a hydrophilic monomer 2, 2-dimethylolbutyric acid, neutralization of triethylamine and water dispersion; modifying gelatin by urea and sodium dodecyl sulfate to obtain gelatin liquefact with high solid content and low viscosity; uniformly spraying an alkali solution into the fenugreek gum, uniformly mixing, drying, cooling and crushing to obtain fenugreek gum powder subjected to alkali heat treatment; uniformly mixing and stirring the castor oil-based waterborne polyurethane, the gelatin liquefied product, the polyamide epichlorohydrin and the alkali-heat-treated fenugreek gum powder at normal temperature to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
2. The preparation method of the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 1, wherein,
the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive is prepared by the following steps:
1) according to the mass parts, firstly, fully stirring and mixing 100-300 parts of gelatin liquefied material and 15-60 parts of cross-linking agent polyamide epichlorohydrin;
2) adding 100 portions of castor oil water polyurethane and 300 portions, fully stirring and mixing;
3) finally, 20-100 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive.
3. The preparation method of the castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive according to claim 1 or 2, wherein,
the solid content of the castor oil-based waterborne polyurethane is 30-36%; the solid content of the gelatin liquefact is 35-60%; the mass fraction of the alkali solution is 30-50%; the solid content of the polyamide epichlorohydrin is 12.5-20%.
4. The preparation method of the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 3, wherein the castor oil-based aqueous polyurethane is obtained by a method comprising the following steps:
1) according to the mass percent, adding 170 parts of castor oil, 120-170 parts of isophorone diisocyanate, 150 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate into a reaction kettle, reacting at the temperature of 60-70 ℃ and the rotating speed of 200-400rpm for 2.5-3.5 h;
2) slowly adding 30-55 parts of triethylamine into the reaction kettle, and stirring for 0.5-1 h;
3) adding 900 parts of 500-1200 rpm water for dispersion, adjusting the rotation speed to 1000-1200rpm, and stirring for 0.5-1h to obtain the castor oil-based waterborne polyurethane.
5. The preparation method of the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 3, wherein the gelatin liquefact is obtained by a method comprising the following steps:
1) adding 100 parts of water, 5-8 parts of urea and 2-4 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving, and heating to 75-80 ℃;
2) and then slowly adding 55-150 parts of gelatin (the gelatin is added within 15 minutes), stirring for 1-1.5 hours until the gelatin is completely dissolved, and finally cooling the product to room temperature to obtain a gelatin liquefied product.
6. The method for preparing the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 3, wherein the alkali-heat-treated fenugreek gum powder is obtained by a method comprising the following steps:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 2-6 parts of an alkali solution, and uniformly mixing;
2) drying the product obtained in the step 1 in an oven at the temperature of 90-120 ℃ for 60-180 min;
3) and (3) drying the product obtained in the step (2) at 65 ℃ until the water content is 6-9%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder.
7. The preparation method of the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 6, wherein the alkali solution in the step 2 is a sodium hydroxide solution or a potassium hydroxide solution.
8. The preparation method of the castor oil-based aqueous polyurethane/gelatin interpenetrating network adhesive according to claim 3, wherein the preparation method specifically comprises the following steps:
step one, preparing castor oil-based waterborne polyurethane:
1) according to the mass percent, adding 170 parts of castor oil, 120-170 parts of isophorone diisocyanate, 150 parts of 2, 2-dimethylolbutyric acid and 1 part of dibutyl dilaurate into a reaction kettle, reacting at the temperature of 60-70 ℃ and the rotating speed of 200-400rpm for 2.5-3.5 h;
2) slowly adding 30-55 parts of triethylamine into the reaction kettle, and stirring for 0.5-1 h;
3) adding 900 parts of 500-1200 rpm water for dispersion, adjusting the rotation speed to 1000-1200rpm, and stirring for 0.5-1h to obtain the castor oil-based waterborne polyurethane with the solid content of 30-36%;
step two, preparing a gelatin liquefaction product:
1) adding 100 parts of water, 5-8 parts of urea and 2-4 parts of sodium dodecyl sulfate into a reaction kettle by mass, stirring for dissolving, and heating to 75-80 ℃;
2) then slowly adding 55-150 parts of gelatin (the gelatin is added within 15 minutes) into the reaction kettle, stirring for 1-1.5 hours until the gelatin is completely dissolved, and finally cooling the product to room temperature to obtain a gelatin liquefaction product with the solid content of 35-60%;
step three, preparing the fenugreek gum powder subjected to alkali heat treatment:
1) weighing 15 parts of fenugreek gum by mass, adding the fenugreek gum into a high-speed stirrer, uniformly spraying 2-6 parts of sodium hydroxide or potassium hydroxide solution (the mass fraction is 30% -50%), and uniformly mixing;
2) drying the product obtained in the step one in an oven at the temperature of 90-120 ℃ for 60-180 min;
3) drying the product obtained in the second step at 65 ℃ until the water content is 6-9%, cooling and grinding to obtain alkali-heat treated fenugreek gum powder;
step four, preparing the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive:
1) according to the mass parts, firstly, fully stirring and mixing 100-300 parts of gelatin liquefied material and 15-60 parts of cross-linking agent polyamide epichlorohydrin (the solid content is 12.5% -20%);
2) adding 100 parts of castor oil-based waterborne polyurethane and 300 parts of castor oil-based waterborne polyurethane, and fully stirring and mixing;
3) finally, 20-100 parts of alkali-heat treated fenugreek gum powder is added; and uniformly stirring to obtain the castor oil-based waterborne polyurethane/gelatin interpenetrating network polymer adhesive.
9. The castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive prepared by the preparation method of claim 1.
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| CN114591713A (en) * | 2022-02-25 | 2022-06-07 | 陕西科技大学 | Method for preparing adhesive by utilizing waterborne polyurethane modified industrial gelatin |
| CN115141597A (en) * | 2022-08-04 | 2022-10-04 | 河南工程学院 | Castor oil-based degradable pressure-sensitive adhesive and preparation method thereof |
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| CN107189746A (en) * | 2017-06-15 | 2017-09-22 | 广东药科大学 | A kind of active polyurethane medical adhesive and preparation method thereof |
| WO2017177578A1 (en) * | 2016-04-14 | 2017-10-19 | 久盛地板有限公司 | Recombined wooden board using polyimide-modified polyurethane adhesive and preparation method therefor |
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| CN104761699A (en) * | 2015-04-16 | 2015-07-08 | 陕西科技大学 | Method for preparing carboxyl-containing castor oil modified waterborne polyurethane |
| WO2017177578A1 (en) * | 2016-04-14 | 2017-10-19 | 久盛地板有限公司 | Recombined wooden board using polyimide-modified polyurethane adhesive and preparation method therefor |
| CN107189746A (en) * | 2017-06-15 | 2017-09-22 | 广东药科大学 | A kind of active polyurethane medical adhesive and preparation method thereof |
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| CN114591713A (en) * | 2022-02-25 | 2022-06-07 | 陕西科技大学 | Method for preparing adhesive by utilizing waterborne polyurethane modified industrial gelatin |
| CN115141597A (en) * | 2022-08-04 | 2022-10-04 | 河南工程学院 | Castor oil-based degradable pressure-sensitive adhesive and preparation method thereof |
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