CN114591713A - Method for preparing adhesive by utilizing waterborne polyurethane modified industrial gelatin - Google Patents
Method for preparing adhesive by utilizing waterborne polyurethane modified industrial gelatin Download PDFInfo
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- CN114591713A CN114591713A CN202210184007.8A CN202210184007A CN114591713A CN 114591713 A CN114591713 A CN 114591713A CN 202210184007 A CN202210184007 A CN 202210184007A CN 114591713 A CN114591713 A CN 114591713A
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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
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention discloses a method for preparing an adhesive by utilizing waterborne polyurethane modified industrial gelatin, which comprises the following steps: firstly, preparing waterborne polyurethane and an epoxy compound, then mixing gelatin and water, stirring until the gelatin is completely dissolved, carrying out alkaline hydrolysis, adding sodium dodecyl sulfate, stirring uniformly, dropwise adding the epoxy compound for reaction to obtain the epoxy compound-gelatin, and finally reacting the waterborne polyurethane and the epoxy compound-gelatin to obtain the waterborne polyurethane modified gelatin adhesive. Through Diels-Alder cycloaddition reaction of click chemistry, a diolefin system of the waterborne polyurethane and FGE-gelatin reacts to generate a stable six-membered ring structure, so that crosslinking and curing of the gelatin and the waterborne polyurethane are effectively enhanced. Meanwhile, due to the crosslinking reaction, the performances of the gelatin in the aspects of low mechanical property, low water resistance and the like are improved, and the problem of low bonding speed of the conventional gelatin adhesive is also solved.
Description
Technical Field
The invention belongs to the technical field of adhesive preparation, and particularly relates to a method for preparing an adhesive by using aqueous polyurethane modified industrial gelatin.
Background
In recent years, the yield of leather-making enterprises and leather in China is rapidly increased, but the problem of environmental pollution is increasingly serious, according to statistics, more than 140 million tons of solid wastes are generated in the leather-making industry every year, more than 80 percent of the wastes are formed by collagen, and gelatin is formed by degrading collagen in the leather wastes and has good biodegradability and biocompatibility as a natural biomass material; and the molecular chain of the gelatin has rich carboxyl, amino, hydroxyl and other active groups, so that the epoxy group can easily carry out chemical modification on the gelatin, thereby improving the hot-sticking and cold-brittleness performance of the gelatin and endowing new performance.
Meanwhile, the waterborne polyurethane is an environment-friendly material using water as a dispersing agent, a molecular chain contains macromolecules of carbamate groups and hydrophilic groups, and the waterborne polyurethane has the advantages of safety, no toxicity or low toxicity, no solvent residue and the like, and the application of the waterborne polyurethane to a modified adhesive is a current research hotspot. Aiming at the application of leather shoes and bags, the aqueous polyurethane modified gelatin has the advantages of adjustable mechanical property, excellent bonding property, environmental friendliness and the like. The amino on the gelatin reacts with the isocyanate group of the waterborne polyurethane, so that the crosslinking degree is increased, and the bonding speed is improved. However, the isocyanate group is highly reactive and needs to be blocked for protection. Click chemistry has the advantages of simple reaction conditions, good stereoselectivity, no toxic by-products, single product and the like. Therefore, crosslinking and curing are promoted through a click chemical reaction, the purpose of improving the bonding performance of the adhesive is achieved, and the application of the gelatin-based water-based adhesive in the fields of bags and shoes is promoted.
Disclosure of Invention
The invention aims to provide a method for preparing an adhesive by using aqueous polyurethane modified industrial gelatin, which improves the bonding property of the adhesive.
The technical scheme adopted by the invention is that a method for preparing an adhesive by utilizing water-based polyurethane modified industrial gelatin is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane;
step 2, preparing an epoxy compound;
step 3, preparing an epoxy compound-gelatin;
and 4, mixing the waterborne polyurethane and the epoxy compound-gelatin, and placing the mixture into a reactor for reaction to obtain the waterborne polyurethane modified gelatin adhesive.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
mixing isophorone diisocyanate, polytetrahydrofuran and dibutyltin dilaurate, placing the mixture into a reactor, and reacting under the protection of nitrogen at the temperature of 70-90 ℃ for 1.5-3 h; and adding dimethylolpropionic acid and acetone, continuing to react for 2-4h, adding N- (4-hydroxyphenyl) maleimide and acetone, cooling to 60-80 ℃, reacting for 2-4h, finally adding triethylamine aqueous solution into the reaction system, cooling to room temperature, stirring at high speed, and reacting for 1-2h to obtain the end-capped waterborne polyurethane.
The molar ratio of isophorone diisocyanate, polytetrahydrofuran, dibutyltin dilaurate, dimethylolpropionic acid and N- (4-hydroxyphenyl) maleimide is 4-8: 2-5: 0.01-0.05: 1-2: 1-2; the triethylamine aqueous solution is prepared by mixing the components in a volume ratio of 1: 150-200 of triethylamine and deionized water.
In the step 2, the method specifically comprises the following steps:
placing epoxy chloropropane and tetrabutylammonium hydrogen sulfate in a reactor, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding furfuryl alcohol, reacting in an ice-water bath after dropwise adding, wherein the reaction time is 3-6h, dropwise adding a sodium hydroxide solution, continuously reacting in the ice-water bath for 1-3h, extracting and purifying through anhydrous ether and water after the reaction is completed, and obtaining the epoxy compound as an oil phase.
In step 3, the method specifically comprises the following steps:
mixing gelatin and deionized water, standing at room temperature for 30min until the gelatin is swelled, heating to 35-55 ℃, stirring until the gelatin is completely dissolved and hydrolyzed for 30min, adjusting the pH of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, carrying out alkaline hydrolysis for 30min, adding sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding FGE, and reacting at the temperature of 50-80 ℃ for 2-4h to obtain the epoxy compound-gelatin.
In the step 4, the reaction temperature is 60-80 ℃, and the reaction time is 18-36 h.
The invention has the beneficial effects that: the adhesive prepared by modifying industrial gelatin with aqueous polyurethane is adopted, and the Diels-Alder cycloaddition reaction of click chemistry is adopted to react the aqueous polyurethane with a diolefin system of FGE-gelatin to generate a stable six-membered ring structure, so that the crosslinking and curing of the gelatin and the aqueous polyurethane are effectively enhanced. Meanwhile, due to the crosslinking reaction, the performances of the gelatin in the aspects of low mechanical property, low water resistance and the like are improved, and the problem of low bonding speed of the conventional gelatin adhesive is also solved.
Drawings
FIG. 1 is a reaction scheme of an aqueous polyurethane (MWPU) in the process of the present invention;
FIG. 2 is a reaction scheme of epoxy compounds (FGE) in the process of the present invention;
FIG. 3 is a reaction diagram of the aqueous polyurethane modified gelatin adhesive in the method of the present invention;
FIG. 4 is an infrared characterization of MWPU prepared by the process of the present invention;
FIG. 5 is a graph of an infrared characterization of FGE prepared by the process of the present invention;
FIG. 6 is an infrared representation of the aqueous polyurethane modified gelatin adhesive prepared by the method of the present invention;
FIG. 7 is a graph comparing the tensile shear strength of the adhesives of the invention with other adhesives;
FIG. 8 is a graph comparing the T-peel strength of the adhesives of the invention with other adhesives;
fig. 9 is a comparison of the water contact angle of the adhesive of the present invention with other adhesives.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for preparing an adhesive by utilizing aqueous polyurethane modified industrial gelatin, which is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane (MWPU), as shown in FIG. 1, specifically:
mixing isophorone diisocyanate, polytetrahydrofuran and dibutyltin dilaurate, placing the mixture into a reactor, and reacting under the protection of nitrogen at the temperature of 70-90 ℃ for 1.5-3 h; adding dimethylolpropionic acid and acetone (reducing the viscosity of the system), continuously reacting for 2-4h, then adding N- (4-hydroxyphenyl) maleimide and acetone, cooling to 60-80 ℃, reacting for 2-4h, finally adding triethylamine aqueous solution into the reaction system, cooling to room temperature, stirring at high speed, and reacting for 1-2h to obtain the terminated waterborne polyurethane;
the molar ratio of isophorone diisocyanate, polytetrahydrofuran, dibutyltin dilaurate, dimethylolpropionic acid and N- (4-hydroxyphenyl) maleimide is 4-8: 2-5: 0.01-0.05: 1-2: 1-2;
the triethylamine aqueous solution is prepared by mixing the components in a volume ratio of 1: 150-200 triethylamine and deionized water;
step 2, preparing an epoxy compound (FGE), as shown in fig. 2, specifically:
placing epoxy chloropropane and tetrabutylammonium hydrogen sulfate in a reactor, stirring until tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding furfuryl alcohol, reacting in an ice-water bath after dropwise adding, wherein the reaction temperature of the ice-water bath is 0-15 ℃, the reaction time is 3-6h, dropwise adding a sodium hydroxide solution, continuously reacting in the ice-water bath for 1-3h, extracting and purifying through anhydrous ether and water after the reaction is completed, and obtaining an oil phase which is an epoxy compound FGE;
the mol ratio of the epichlorohydrin to the furfuryl alcohol is 0.8-1.2: 1, the mass ratio of tetrabutylammonium hydrogen sulfate to sodium hydroxide is 1: 15-25;
the mass fraction of the sodium hydroxide solution is 50 percent;
step 3, preparing epoxy compound-gelatin (FGE-gelatin), specifically:
mixing gelatin and deionized water, standing at room temperature for 30min until the gelatin is swelled, heating to 35-55 ℃, stirring until the gelatin is completely dissolved and hydrolyzed for 30min, adjusting the pH of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, performing alkaline hydrolysis for 30min, then adding sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding FGE, and reacting at the temperature of 50-80 ℃ for 2-4h to obtain FGE-gelatin;
the mass ratio of the gelatin to the deionized water is 1: 3-9; the mass ratio of the sodium dodecyl sulfate to the gelatin is 1: 5-15;
and 4, as shown in figure 3, mixing the waterborne polyurethane MWPU and the FGE-gelatin, placing the mixture into a reactor, and reacting at the temperature of 60-80 ℃ for 18-36h to obtain the waterborne polyurethane modified gelatin adhesive.
The mass ratio of MWPU to FGE-gelatin is 1-10: 1-10.
FIG. 4 is an infrared characterization plot of MWPU, wherein the peak positions represented by the different wavenumbers are shown in Table 1. At 2260cm-1The peak is the characteristic absorption peak of-NCO, and the spectrogram does not appear, which indicates that the-NCO reaction is complete, and in conclusion, the MWPU is successfully prepared.
TABLE 1 Peak position represented by different wavenumbers
FIG. 5 is an infrared characterization plot of FGE, where the peak positions are represented by different wavenumbers as shown in Table 2. These absorption peaks, which are both present on Furfural (FA), are characteristic absorption peaks of FGE, and taken together, indicate that FGE was successfully prepared.
TABLE 2 Peak positions represented by different wavenumbers
Fig. 6 is an infrared characterization diagram of the aqueous polyurethane modified gelatin adhesive, wherein the peak positions represented by different wave numbers are shown in table 3. And 1100cm-1Is a C-O stretching vibration absorption peak on a furan ring, appears on FGE/GE, and does not appear on the modified adhesive. In conclusion, it is shown that the aqueous polyurethane modified gelatin adhesive is successfully prepared.
TABLE 3 Peak positions represented by different wavenumbers
| Wave number/cm-1 | Peak position |
| 1730cm-1 | Absorption peak of C ═ O stretching vibration in carbamate |
| 1660cm-1 | Absorption peak of amide i band (carbonyl C ═ O stretching vibration) |
| 1530cm-1 | Absorption peak of amide II band (C-N-H bending vibration) |
| 1228cm-1 | Absorption peak of amide III band (C-N stretching vibration) |
Fig. 7 is a comparison graph of the tensile shear strength of the adhesive of the present invention and other adhesives, and it can be seen that the tensile shear strength of the sample treated with the adhesive is greatly improved, and the sample has good adhesive property.
FIG. 8 is a comparison graph of T-peel strength between the adhesive of the present invention and other adhesives, and it can be seen that the T-peel strength of the samples treated with the adhesive is improved to some extent, and the samples have good adhesive properties.
Fig. 9 is a comparison graph of water contact angles of the adhesive of the present invention and other adhesives, and it can be seen that the water contact angle of the sample treated with the adhesive is greatly increased, and the sample has good hydrophobic property and certain water resistance.
Example 1
The invention relates to a method for preparing an adhesive by utilizing aqueous polyurethane modified industrial gelatin, which is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane (MWPU), specifically:
taking 0.018mol of isophorone diisocyanate, 0.01mol of polytetrahydrofuran (baked for 2h at 80 ℃ in an oven), and 2 drops of dibutyltin dilaurate in a three-neck flask, heating to 80 ℃ under the protection of nitrogen, and reacting for 2 h; adding 0.7001g dimethylolpropionic acid and a proper amount of acetone (reducing the viscosity of the system) and reacting for 3 h; then adding 0.003mol of N- (4-hydroxyphenyl) maleimide and acetone, cooling to 75 ℃ and reacting for 3 h; finally, dissolving 0.005mol of triethylamine in 60mL of deionized water, adding the solution into a reaction system, cooling to room temperature, stirring at a high speed, and reacting for 1.5 h;
step 2, preparing an epoxy compound (FGE), specifically:
and (2) taking 1.1mol of epichlorohydrin and 4g of tetrabutylammonium hydrogen sulfate in a three-neck flask, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding 1mol of furfuryl alcohol, reacting in an ice-water bath for 4 hours after dropwise adding, dropwise adding 160mL of 50% sodium hydroxide solution, and reacting in the ice-water bath for 2 hours. After the reaction is finished, the mixture is extracted and purified by anhydrous ether and water, and the oil phase is the obtained epoxy compound FGE.
Step 3, preparing epoxy compound-gelatin (FGE-gelatin), specifically:
adding 12g gelatin into 68mL deionized water, standing at room temperature for 30min until the gelatin swells, heating to 40 deg.C, stirring to completely dissolve the gelatin, and hydrolyzing for 30 min. And (3) adjusting the pH value of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, and performing alkaline hydrolysis for 30 min. Adding 1.2g of sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding 3g of FGE, and reacting for 2h at 60 ℃.
Step 4, taking 5g of waterborne polyurethane MWPU and 50g of FGE-gelatin in a three-neck flask, heating to 70 ℃, and reacting for 24 hours;
the synthesized adhesive is tested for tensile shear strength according to GB/T7124-2008, and the obtained tensile shear strength is 0.839MPa, and the T-peel strength is 1.241N/mm.
Example 2
The invention relates to a method for preparing an adhesive by utilizing aqueous polyurethane modified industrial gelatin, which is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane (MWPU), specifically:
taking 0.018mol of isophorone diisocyanate, 0.01mol of polytetrahydrofuran (baked for 2h at 80 ℃ in an oven), and 2 drops of dibutyltin dilaurate in a three-neck flask, heating to 90 ℃ under the protection of nitrogen, and reacting for 3 h; then 0.7001g dimethylolpropionic acid and a proper amount of acetone are added (the viscosity of the system is reduced), and the reaction is carried out for 2.5 h; then adding 0.003mol of N- (4-hydroxyphenyl) maleimide and acetone, cooling to 70 ℃ and reacting for 2.5 h; finally, dissolving 0.005mol of triethylamine in 60mL of deionized water, adding the solution into a reaction system, cooling to room temperature, stirring at a high speed, and reacting for 2 hours;
step 2, preparing an epoxy compound (FGE), specifically:
and (2) taking 1.1mol of epichlorohydrin and 4g of tetrabutylammonium hydrogen sulfate in a three-neck flask, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding 1mol of furfuryl alcohol, reacting in an ice-water bath for 5 hours after dropwise adding, dropwise adding 160mL of 50% sodium hydroxide solution, and reacting in the ice-water bath for 2.5 hours. After the reaction is finished, the mixture is extracted and purified by anhydrous ether and water, and the oil phase is the obtained epoxy compound FGE.
Step 3, preparing epoxy compound-gelatin (FGE-gelatin), specifically:
adding 12g gelatin into 108mL deionized water, standing at room temperature for 30min until the gelatin swells, heating to 50 deg.C, stirring to completely dissolve the gelatin, and hydrolyzing for 30 min. And (3) adjusting the pH value of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, and performing alkaline hydrolysis for 30 min. Adding 1.2g of sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding 3g of FGE, and reacting at 70 ℃ for 2.5 h;
and step 4, taking 5g of waterborne polyurethane MWPU and 50g of FGE-gelatin in a three-neck flask, heating to 70 ℃, and reacting for 18 h. The synthesized adhesive is tested for tensile shear strength according to GB/T7124-2008, and the obtained tensile shear strength is 0.433MPa and the T-peel strength is 0.694N/mm.
Example 3
The invention discloses a method for preparing an adhesive by utilizing waterborne polyurethane modified industrial gelatin, which is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane (MWPU), specifically:
taking 0.015mol of isophorone diisocyanate, 0.01mol of polytetrahydrofuran (dried for 2 hours at 80 ℃ in a drying oven) and 2 drops of dibutyltin dilaurate into a three-neck flask, heating to 70 ℃ under the protection of nitrogen, and reacting for 3 hours; then adding 0.6667g of dimethylolpropionic acid and a proper amount of acetone (reducing the viscosity of the system) and reacting for 3 hours; then adding 0.0001mol of N- (4-hydroxyphenyl) maleimide and acetone, cooling to 65 ℃ and reacting for 3 h; finally, dissolving 0.005mol of triethylamine in 60mL of deionized water, adding the solution into a reaction system, cooling to room temperature, stirring at a high speed, and reacting for 2 hours;
step 2, preparing an epoxy compound (FGE), specifically:
and (2) taking 1.1mol of epichlorohydrin and 4g of tetrabutylammonium hydrogen sulfate in a three-neck flask, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding 1mol of furfuryl alcohol, reacting in an ice-water bath for 4 hours after dropwise adding, dropwise adding 160mL of 50% sodium hydroxide solution, and reacting in the ice-water bath for 3 hours. After the reaction is finished, the mixture is extracted and purified by anhydrous ether and water, and the oil phase is the obtained epoxy compound FGE.
Step 3, preparing epoxy compound-gelatin (FGE-gelatin), specifically:
adding 12g gelatin into 68mL deionized water, standing at room temperature for 30min until the gelatin swells, heating to 50 deg.C, stirring to completely dissolve the gelatin, and hydrolyzing for 30 min. And (3) adjusting the pH value of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, and performing alkaline hydrolysis for 30 min. Adding 1.2g of sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding 3.6g of FGE, and reacting for 3h at 80 ℃;
and 4, taking 5g of waterborne polyurethane MWPU and 50g of FGE-gelatin in a three-neck flask, heating to 65 ℃, and reacting for 18 h. The synthesized adhesive is tested for tensile shear strength according to GB/T7124-2008, and the obtained tensile shear strength is 0.527MPa and the T-peel strength is 0.812N/mm.
Example 4
The invention relates to a method for preparing an adhesive by utilizing aqueous polyurethane modified industrial gelatin, which is implemented according to the following steps:
step 1, preparing end-capped waterborne polyurethane (MWPU), specifically:
taking 0.018mol of isophorone diisocyanate, 0.01mol of polytetrahydrofuran (baked for 2h at 80 ℃ in an oven), and 2 drops of dibutyltin dilaurate in a three-neck flask, heating to 80 ℃ under the protection of nitrogen, and reacting for 2 h; adding 0.7001g dimethylolpropionic acid and a proper amount of acetone (reducing the viscosity of the system) and reacting for 3 h; then adding 0.003mol of N- (4-hydroxyphenyl) maleimide and acetone, cooling to 65 ℃ and reacting for 3.5 h; finally, dissolving 0.0055mol of triethylamine in 60mL of deionized water, adding the solution into a reaction system, cooling to room temperature, stirring at a high speed, and reacting for 2 hours;
step 2, preparing an epoxy compound (FGE), specifically:
taking 1.1mol of epichlorohydrin and 4g of tetrabutylammonium hydrogen sulfate in a three-neck flask, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding 1mol of furfuryl alcohol, reacting in an ice-water bath for 5 hours after dropwise adding, dropwise adding 160mL of sodium hydroxide solution with the mass fraction of 50%, and reacting in the ice-water bath for 2 hours. After the reaction is finished, extracting and purifying through anhydrous ether and water, wherein an oil phase is the obtained epoxy compound FGE;
step 3, preparing epoxy compound-gelatin (FGE-gelatin), specifically:
adding 12g gelatin into 48mL deionized water, standing at room temperature for 30min until the gelatin swells, heating to 45 deg.C, stirring to completely dissolve the gelatin, and hydrolyzing for 30 min. And (3) adjusting the pH value of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, and performing alkaline hydrolysis for 30 min. Adding 1.2g of sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding 2.4g of FGE, and reacting for 3h at 55 ℃;
and 4, taking 5g of waterborne polyurethane MWPU and 50g of FGE-gelatin in a three-neck flask, heating to 70 ℃, and reacting for 24 hours. The synthesized adhesive is tested for tensile shear strength according to GB/T7124-2008, and the obtained tensile shear strength is 0.465MPa and the T-peel strength is 0.739N/mm.
Claims (6)
1. A method for preparing an adhesive by utilizing waterborne polyurethane modified industrial gelatin is characterized by comprising the following steps:
step 1, preparing end-capped waterborne polyurethane;
step 2, preparing an epoxy compound;
step 3, preparing an epoxy compound-gelatin;
and 4, mixing the waterborne polyurethane and the epoxy compound-gelatin, and placing the mixture into a reactor for reaction to obtain the waterborne polyurethane modified gelatin adhesive.
2. The method for preparing the adhesive by using the aqueous polyurethane modified industrial gelatin according to claim 1, wherein in the step 1, the method specifically comprises the following steps:
mixing isophorone diisocyanate, polytetrahydrofuran and dibutyltin dilaurate, placing the mixture into a reactor, and reacting under the protection of nitrogen at the temperature of 70-90 ℃ for 1.5-3 h; and adding dimethylolpropionic acid and acetone, continuing to react for 2-4h, then adding N- (4-hydroxyphenyl) maleimide and acetone, cooling to 60-80 ℃, reacting for 2-4h, finally adding triethylamine aqueous solution into the reaction system, cooling to room temperature, stirring at high speed, and reacting for 1-2h to obtain the end-capped waterborne polyurethane.
3. The method for preparing the adhesive by utilizing the aqueous polyurethane modified industrial gelatin as claimed in claim 2, wherein the molar ratio of isophorone diisocyanate, polytetrahydrofuran, dibutyltin dilaurate, dimethylolpropionic acid and N- (4-hydroxyphenyl) maleimide is 4-8: 2-5: 0.01-0.05: 1-2: 1-2; the triethylamine aqueous solution is prepared by mixing the components in a volume ratio of 1: 150-200 of triethylamine and deionized water.
4. The method for preparing the adhesive by using the aqueous polyurethane modified industrial gelatin according to claim 1, wherein in the step 2, the method specifically comprises the following steps:
placing epoxy chloropropane and tetrabutylammonium hydrogen sulfate in a reactor, stirring until the tetrabutylammonium hydrogen sulfate is completely dissolved, slowly dropwise adding furfuryl alcohol, reacting in an ice-water bath after dropwise adding, wherein the reaction time is 3-6h, dropwise adding a sodium hydroxide solution, continuously reacting in the ice-water bath for 1-3h, extracting and purifying through anhydrous ether and water after the reaction is completed, and obtaining the epoxy compound as an oil phase.
5. The method for preparing the adhesive by using the aqueous polyurethane modified industrial gelatin according to claim 1, wherein in the step 3, the specific steps are as follows:
mixing gelatin and deionized water, standing at room temperature for 30min until the gelatin is swelled, heating to 35-55 ℃, stirring until the gelatin is completely dissolved and hydrolyzed for 30min, adjusting the pH of the gelatin hydrolysate to 8 by using a sodium hydroxide solution with the mass fraction of 10%, carrying out alkaline hydrolysis for 30min, adding sodium dodecyl sulfate into the gelatin alkaline hydrolysis solution, stirring uniformly, slowly dropwise adding FGE, and reacting at the temperature of 50-80 ℃ for 2-4h to obtain the epoxy compound-gelatin.
6. The method for preparing the adhesive by using the aqueous polyurethane modified industrial gelatin as claimed in claim 1, wherein in the step 4, the reaction temperature is 60-80 ℃ and the reaction time is 18-36 h.
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| JP2912658B2 (en) * | 1990-02-13 | 1999-06-28 | 新田ゼラチン株式会社 | Modified synthetic resin composition, modified synthetic resin film, modified cloth, modified paint and modified adhesive |
| CN108949097B (en) * | 2018-06-12 | 2020-07-21 | 陕西科技大学 | Industrial gelatin-enclosed water-based polyurethane adhesive composition and construction method thereof |
| CN110358497B (en) * | 2019-07-09 | 2020-10-16 | 陕西科技大学 | Hyperbranched modified gelatin adhesive for shoes or bags and preparation method thereof |
| CN113292962A (en) * | 2021-06-18 | 2021-08-24 | 陕西科技大学 | Castor oil-based waterborne polyurethane/gelatin interpenetrating network adhesive and preparation method thereof |
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