CN108949097B - Industrial gelatin-enclosed water-based polyurethane adhesive composition and construction method thereof - Google Patents
Industrial gelatin-enclosed water-based polyurethane adhesive composition and construction method thereof Download PDFInfo
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- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention relates to a preparation method of an industrial gelatin crosslinked closed type waterborne polyurethane wood adhesive. Industrial gelatin from tanning solid waste is dissolved in deionized water to swell, and heated to be completely dissolved to obtain gelatin water solution with certain concentration. And adding a certain amount of closed waterborne polyurethane emulsion into the solution, and uniformly stirring at normal temperature to obtain the gelatin-closed waterborne polyurethane wood adhesive. The water resistance and the bonding strength of the wood adhesive can be improved by using the closed waterborne polyurethane crosslinked industrial gelatin as the wood adhesive.
Description
Technical Field
The invention relates to the technical field of aqueous polyurethane adhesives, in particular to an industrial gelatin-enclosed aqueous polyurethane adhesive composition and a construction method thereof.
Background
With the change of the structure of wood raw materials, the supply of wood materials in China has been changed from solid wood to glued wood. Most of the existing wood products are made of artificial boards. According to statistics of the national forestry bureau, the yield of the artificial board in China reaches 3624 thousands of years, and the yield accounts for more than 60 percent of the yield of the artificial board in the world. The adhesive plays a role in bonding wood raw materials in the production of artificial boards, and the production of the adhesive for wood is particularly important along with the increase of the production capacity of the artificial boards.
China has abundant raw hide resources and is one of leather-making countries in the world. The tanning industry is a traditional industry characterized by high input of raw materials and low output of products. According to incomplete statistics, 140 million tons of leather leftover wastes are generated in China every year, most of the solid wastes are chromium-free collagen before tanning such as leftover materials and ash leather blocks which are trimmed from raw leather, and chromium-containing collagen wastes generated by shaving and trimming blue leather, and the chromium-free collagen wastes can be directly used for producing gelatin, feed and the like. Based on the method, the industrial gelatin extracted from the waste leather scraps is utilized to synthesize a new product, so that the waste resources are recycled, and the waste is changed into valuable; and the occurrence of toxic capsule and leather milk events is avoided to a certain extent, economic benefits and environmental benefits are achieved, the requirements of clean production and sustainable development are met, and the method has important significance on the sustainable development of the leather-making industry.
Gelatin is used as a natural biomass polymer material with wide source, low price, excellent compatibility and degradability, contains rich amino, hydroxyl, carboxyl and other functional groups on a molecular chain, has certain viscosity, and has certain advantages in the aspect of preparing adhesives. But the wide application of the gelatin is limited by the defects of poor heat resistance, water resistance, mechanical property and the like. Therefore, gelatin must be modified to meet the needs of human society in production and life. Thus not only utilizing waste resources and changing waste into valuable, but also achieving the purpose of protecting the environment; the prepared adhesive has a certain bonding effect and activity of reacting with formaldehyde, and can remove free formaldehyde released by other adhesives, so that the health of human bodies is protected, and the trend of developing real green, environment-friendly and nontoxic wood-based composite materials in the international wood industry is met.
Disclosure of Invention
The invention aims to realize resource utilization of leather solid waste, realize high-value conversion of the leather solid waste, provide an industrial gelatin-enclosed waterborne polyurethane adhesive with good application performance, no pollution and use the adhesive for bonding wood.
The technical scheme adopted by the invention is as follows:
The preparation method of the industrial gelatin-enclosed waterborne polyurethane adhesive is characterized by comprising the following steps:
The method comprises the following steps:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10-20 g of industrial gelatin into 80-90 g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin water solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 64-128 mmol of diisocyanate compound, 20-50 mmol of polyether polyol and 2-3 d of dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 60-70 ℃, and reacting for 1-2 h to obtain a polyurethane prepolymer;
(2) 2.4-12 mmol of oligomer dihydric alcohol chain extender containing hydrophilic group, heating to 70-90 ℃, then cooling to 30-50 ℃, and adding 43-152 mmol of sealing agent to seal the polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 30-40 ℃, adding triethylamine in an amount which is equimolar with the oligomer dihydric alcohol containing a hydrophilic group for neutralization for 20-60 min;
(4) And then adding 2-6 times of deionized water, stirring for 30-60 min under a high-speed shearing action force, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding 10-50% of enclosed waterborne polyurethane by mass of the gelatin aqueous solution into the gelatin (INDE) aqueous solution, and stirring at normal temperature to obtain the industrial gelatin-enclosed waterborne polyurethane (MEKO-WPU) adhesive.
The industrial gelatin used in step one is from tannery solid waste.
The molecular weight of the industrial gelatin in the step one is 15000-250000 Da.
And the diisocyanate compound in the second step is isophorone diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate.
The polyether polyol in the second step is polytetrahydrofuran (Mn = 1000), polyethylene glycol (Mn = 1000) and polypropylene glycol (Mn = 1000).
And the oligomer diol chain extender in the second step is dimethylolpropionic acid or dimethylolbutyric acid.
The blocking agent in the second step is Methyl Ethyl Ketoxime (MEKO).
The amount of the closed waterborne polyurethane used in the step three is 10-50% of the mass of the gelatin aqueous solution.
The industrial gelatin-enclosed water-based polyurethane adhesive obtained by the preparation method.
The adhesive is used for bonding wood.
Uniformly coating the synthesized adhesive on poplar single boards, wherein the adhesive application amount is 300g/m 2And performing hot pressing on the combined blank for 6min at the temperature of 120-150 ℃ and under the pressure of 1.0 MPa.
The invention has the following advantages:
1. The closed waterborne polyurethane prepared by the invention takes water as a dispersing agent, is safe and environment-friendly, and has a certain production and application prospect.
2. Methyl ethyl ketoxime is used for sealing the polyurethane prepolymer, the deblocking temperature is proper, and the system can deblock isocyanate groups during high-temperature hot pressing, so that the isocyanate groups react with active hydrogen and gelatin on the surface of wood to form a denser network crosslinking structure.
3. The raw material utilizes industrial gelatin from waste leather, so that the resource utilization of waste is realized, and the synthesized adhesive has no free formaldehyde release and is a bio-based environment-friendly wood adhesive.
4. The synthesized adhesive can be applied to the bonding of plywood and particle boards.
5. The prepared adhesive has the bonding strength meeting the national II plywood requirement (not less than 0.7 MPa) and has good water resistance.
Drawings
FIG. 1 is a schematic diagram of a shear force test method;
FIG. 2 is an IR spectrum before and after MEKO blocks WPU;
FIG. 3 shows the effect of MEKO-WPU dosage on dry and wet adhesive strength of an adhesive.
Detailed Description
The INGE/MEKO-WPU adhesive is prepared by deblocking-NCO groups in a hot pressing process, so that-NCO reacts with active hydrogen on the gelatin and the wood board to form a network structure. The invention is further illustrated with reference to specific embodiments below.
The first embodiment is as follows:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10g of industrial gelatin into 90g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin aqueous solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 64mmol of isophorone diisocyanate, 40mmol of polypropylene glycol (Mn = 1000) and 2d dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 70 ℃, and reacting for 1h to obtain a polyurethane prepolymer;
(2) Adding 2.4mmol of dimethylolpropionic acid into the system, heating to 80 ℃, then cooling to 50 ℃, and adding 43mmol of methyl ethyl ketoxime to seal the polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 40 ℃, adding triethylamine with the molar quantity equal to that of the oligomer dihydric alcohol containing hydrophilic groups for neutralization for 30 min;
(4) And then adding 3 times of deionized water, stirring for 30min under the action of high-speed shearing, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding 10% of enclosed type aqueous polyurethane based on the mass of the gelatin aqueous solution into the gelatin aqueous solution, and uniformly stirring at normal temperature to obtain the industrial gelatin-enclosed type aqueous polyurethane adhesive.
Step four: uniformly coating the synthesized adhesive on poplar veneers, assembling embryos, then carrying out hot pressing for 6min under the conditions of 150 ℃ and 1.0MPa, and averaging three groups of samples.
The second embodiment:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10g of industrial gelatin into 90g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin aqueous solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 80mmol of isophorone diisocyanate, 40mmol of polypropylene glycol (Mn = 1000) and 2d dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 70 ℃, and reacting for 1h to obtain a polyurethane prepolymer;
(2) Adding 4mmol of dimethylolpropionic acid into the system, heating to 80 ℃, then cooling to 40 ℃, and adding 79mmol of methyl ethyl ketoxime to seal the polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 40 ℃, adding triethylamine with the molar quantity equal to that of the oligomer dihydric alcohol containing hydrophilic groups for neutralization for 30 min;
(4) And then adding 3 times of deionized water, stirring for 30min under the action of high-speed shearing, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding closed waterborne polyurethane accounting for 20% of the mass of the gelatin aqueous solution into the gelatin aqueous solution, and uniformly stirring at normal temperature to obtain the industrial gelatin-closed waterborne polyurethane adhesive.
Step four: uniformly coating the synthesized adhesive on poplar single boards, wherein the adhesive application amount is 300g/m 2，And (3) performing hot pressing on the embryos for 6min at 140 ℃ under the pressure of 1.0MPa, and averaging the three groups of samples.
The third embodiment is as follows:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10g of industrial gelatin into 90g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin aqueous solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 96mmol of isophorone diisocyanate, 40mmol of polypropylene glycol (Mn = 1000) and 3d dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 70 ℃, and reacting for 2h to obtain a polyurethane prepolymer;
(2) Adding 6.8mmol of dimethylolpropionic acid into the system, heating to 80 ℃, then cooling to 45 ℃, and adding 98mmol of methyl ethyl ketoxime to seal the polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 40 ℃, adding triethylamine with the molar quantity equal to that of the oligomer dihydric alcohol containing hydrophilic groups for neutralization for 30 min;
(4) And then adding 3 times of deionized water, stirring for 30min under the action of high-speed shearing, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding 30% of enclosed type aqueous polyurethane based on the mass of the gelatin aqueous solution into the gelatin aqueous solution, and uniformly stirring at normal temperature to obtain the industrial gelatin-enclosed type aqueous polyurethane adhesive.
Step four: uniformly coating the synthesized adhesive on poplar single boards, wherein the adhesive application amount is 300g/m 2And hot pressing the combined embryos for 6min at 150 ℃ and 1.0MPa, and averaging the three groups of samples.
The enclosed aqueous polyurethane prepared in this example was subjected to infrared analysis, and the results are shown in fig. 2. Figure 2 is an ir spectrum before and after MEKO blocks WPU. FIG. 2 shows the IR spectrum of the polyurethane after blocking, 2275cm before blocking -1The absorption peak exists, which is the stretching vibration absorption peak of-NCO, and proves that the-NCO in the system is completely blocked after the blocking agent is added. The MEKO closed waterborne polyurethane is successfully prepared.
The adhesive prepared in the embodiment is subjected to a shear force test according to GB/T17657-1999 (the wood is poplar, the glue application amount is 300g/m 2) And calculating the adhesive strength.
The test results are as follows (3 replicates were run):
| Serial number | 1 | 2 | 3 |
| Dry adhesive strength/MPa | 2.27 | 2.15 | 2.18 |
| Wet adhesive strength/MPa | 0.99 | 0.95 | 0.96 |
The data show that the adhesive strength of the industrial gelatin-enclosed waterborne polyurethane adhesive prepared by the invention meets the requirement of national II-type plywood.
The fourth embodiment is as follows:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10g of industrial gelatin into 90g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin aqueous solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 84mmol of isophorone diisocyanate, 30mmol of polypropylene glycol (Mn = 1000) and 3d dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 70 ℃, and reacting for 1h to obtain a polyurethane prepolymer;
(2) Adding 4.2mmol of dimethylolpropionic acid into the system, heating to 80 ℃, then cooling to 30 ℃, and adding 100mmol of methyl ethyl ketoxime sealing polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 40 ℃, adding triethylamine with the molar quantity equal to that of the oligomer dihydric alcohol containing hydrophilic groups for neutralization for 30 min;
(4) And then adding 5 times of deionized water, stirring for 30min under the action of high-speed shearing, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding 30% of enclosed type aqueous polyurethane based on the mass of the gelatin aqueous solution into the gelatin aqueous solution, and uniformly stirring at normal temperature to obtain the industrial gelatin-enclosed type aqueous polyurethane adhesive.
Step four: uniformly coating the synthesized adhesive on poplar single boards, wherein the adhesive application amount is 300g/m 2And hot pressing the combined embryos for 6min at 130 ℃ and 1.0MPa, and averaging the three groups of samples.
The fifth embodiment:
The method comprises the following steps: preparation of an aqueous solution of industrial gelatin:
Adding 10g of industrial gelatin into 90g of deionized water, swelling for 30min at normal temperature, and heating at 40 ℃ until the industrial gelatin is completely dissolved to obtain a gelatin aqueous solution.
Step two: preparing closed waterborne polyurethane:
(1) Adding 64mmol of isophorone diisocyanate, 20mmol of polypropylene glycol (Mn = 1000) and 2d dibutyltin dilaurate into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, reacting for 20min at 50 ℃, heating to 70 ℃, and reacting for 1.5h to obtain a polyurethane prepolymer;
(2) Adding 8.4mmol of dimethylolpropionic acid into the system, heating to 80 ℃, then cooling to 30 ℃, and adding 79mmol of methyl ethyl ketoxime sealing polyurethane prepolymer;
(3) Keeping the temperature of the obtained system at 40 ℃, adding triethylamine with the molar quantity equal to that of the oligomer dihydric alcohol containing hydrophilic groups for neutralization for 30 min;
(4) And then adding 3 times of deionized water, stirring for 30min under the action of high-speed shearing, and obtaining the closed waterborne polyurethane after the reaction is finished.
Step three: preparing an industrial gelatin-enclosed water-based polyurethane adhesive:
Adding 40% of enclosed type aqueous polyurethane based on the mass of the gelatin aqueous solution into the gelatin aqueous solution, and uniformly stirring at normal temperature to obtain the industrial gelatin-enclosed type aqueous polyurethane adhesive.
Step four: uniformly coating the synthesized adhesive on poplar single boards, wherein the adhesive application amount is 300g/m 2And hot pressing the combined embryos for 6min at 120 ℃ and 1.0MPa, and averaging the three groups of samples.
The sixth implementation case:
Industrial gelatin-blocked waterborne polyurethane adhesives having blocked waterborne polyurethane contents of 0%, 10%, 20%, 30%, 40%, and 50% were prepared according to the procedure described in example three, and samples were tested for dry and wet shear strength according to GB/T17657-1999, giving the results of FIG. 3.
FIG. 3 shows that the addition of MEKO-WPU improves the dry and wet shear strength of INDE, and according to GB/T17657-1999, the prepared adhesive has the wet shear strength of the bonded wood boards larger than 0.7MPa when the MEKO-WPU is used in an amount of 10% and 20%, and meets the use requirements of national class II plywood.
Claims (1)
1. An industrial gelatin-enclosed waterborne polyurethane adhesive composition, comprising:
100 parts by mass of gelatin aqueous solution
The enclosed aqueous polyurethane emulsion accounts for 10 percent or 20 percent of the mass of the gelatin aqueous solution;
The gelatin aqueous solution comprises 10-20 parts by mass of industrial gelatin and 80-90 parts by mass of water;
The closed waterborne polyurethane is obtained by a method comprising the following steps:
Reacting a mixture containing 64-128 mmol of isocyanate, 20-40 mmol of polyether polyol and a catalyst dibutyltin dilaurate at 50 ℃ for 20min, and heating to 60-70 ℃ for reacting for 1-2 h; adding 2.5-12 mmol of carboxylic acid type hydrophilic chain extender, and heating to 70-90 ℃ for reaction; after full reaction, cooling to 30-50 ℃, adding 83-152 mmol of methyl ethyl ketoxime, and fully reacting to obtain closed waterborne polyurethane;
And during the emulsification of the closed waterborne polyurethane, a neutralizing agent triethylamine which is enough to disperse the closed waterborne polyurethane into uniform emulsion is also added.
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| CN106753159A (en) * | 2016-11-16 | 2017-05-31 | 四川大学 | One kind degraded polyurethane aqueous wood adhesive of collagen 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 |
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