CN113150309A - Method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose - Google Patents
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention relates to the technical field of material modification, and discloses a method for modifying an anionic waterborne polyurethane emulsion by carboxyl nanocellulose, which comprises the following steps: 1) oxidizing microcrystalline cellulose by using sodium persulfate to prepare carboxyl nano-cellulose to form carboxyl nano-cellulose dispersion liquid; 2) mixing the carboxyl nano cellulose dispersion liquid obtained in the step 1) with an anionic waterborne polyurethane emulsion; 3) and (3) carrying out ultrasonic treatment on the carboxyl nano-cellulose dispersion liquid obtained in the step 2) and the anionic waterborne polyurethane mixed emulsion to obtain the stable carboxyl nano-cellulose modified anionic waterborne polyurethane emulsion. The invention has the advantages of simple preparation process and easy industrial production; according to the invention, the carboxyl nanocellulose is added into the anionic waterborne polyurethane, so that the mechanical property and the water resistance of the polyurethane can be further improved.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to a method for modifying an anionic waterborne polyurethane emulsion by carboxyl nanocellulose.
Background
Nanocellulose refers to biomass cellulose material with a fibre diameter below 100nm, which is mainly derived from elementary fibrils, protofibrils and microfibrils in the cell wall of the biomass material. The nano-cellulose has the advantages of nano-scale, high crystallinity, high Young modulus, high specific surface area, low thermal expansion coefficient, good biodegradability and the like, so the nano-cellulose has wide application fields. The nano-cellulose is often used as a nano-filling material for a reinforced matrix of a composite material, and can obviously improve the mechanical property, the thermal stability and the like of the composite material.
The waterborne polyurethane uses water as a dispersion medium to replace an organic solvent, has the excellent performance of solvent type polyurethane, and also has the performances of oil resistance, low temperature resistance, flex resistance, chemical resistance, safety and reliability, safety and non-flammability and non-toxicity in the construction process, no environmental pollution and the like, and the product is successfully applied to the industries of light textile, leather, wood processing, building, papermaking, coating, adhesive and the like. However, the waterborne polyurethane using water as a medium has a large surface tension and a high enthalpy, so that the film formed by the waterborne polyurethane is poorly compounded with a base material when the waterborne polyurethane is applied, and the mechanical property is reduced.
If the aqueous polyurethane is directly compounded with the nanocellulose, the interface effect between the nanocellulose and the polyurethane is obvious, so that the reinforcing effect of the nanocellulose on the aqueous polyurethane is very limited, and only a small amount of nanocellulose can be added when the comprehensive performance is considered. On the other hand, there are many types of aqueous polyurethane, and they are classified into anionic aqueous polyurethane (carboxylic acid type and sulfonic acid type), cationic aqueous polyurethane (ammonium ion) and nonionic aqueous polyurethane according to the charge performance of hydrophilic functional groups carried by the aqueous polyurethane. In view of the composite compatibility with other materials, it is generally preferable to add a substance having a similar charge property as its reinforcing material. And hydrogen bond bonding is easily formed between hydroxyl groups on the surface of the nano-cellulose, so that the nano-cellulose is easy to generate a self-aggregation phenomenon, the dispersibility of the nano-cellulose in a non-polar matrix is poor, the interface compatibility between the nano-cellulose and the matrix is not good, and the characteristics of the nano-particles are difficult to exert, thereby limiting the application range of the nano-cellulose used for the composite material reinforced material.
In order to solve the above problems, researchers have prepared carboxyl nanocellulose, with which anionic aqueous polyurethane emulsions are modified. The surface of the carboxyl nano-cellulose also contains carboxyl anions, the aqueous polyurethane emulsion is dispersed by adopting anions (carboxylic acid type or sulfonic acid type), and both the carboxyl nano-cellulose and the aqueous polyurethane emulsion contain anions, so that the compatibility is enhanced, the interface effect between the nano-cellulose and the polyurethane can be effectively reduced, and the nano-cellulose and the polyurethane can be better dispersed in the polymer. The carboxylated nano-cellulose has the characteristics of high strength, nano-scale effect and the like of the nano-cellulose, has enhanced hydrophilicity compared with the nano-cellulose, has a negative charge on the surface, is compounded with sulfonic acid type or carboxylic acid type waterborne polyurethane, has greatly improved dispersion stability, can obviously improve the interface compatibility of the nano-cellulose and a polyurethane material, and enhances the mechanical property of the composite material.
Disclosure of Invention
The invention aims to provide a method for modifying an anionic waterborne polyurethane emulsion by carboxyl nanocellulose, and the obtained waterborne polyurethane emulsion has good mechanical property and water resistance.
The invention provides a method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose, which comprises the following steps:
1) oxidizing microcrystalline cellulose by using sodium persulfate to prepare carboxyl nano-cellulose to form carboxyl nano-cellulose dispersion liquid;
2) mixing the carboxyl nano cellulose dispersion liquid obtained in the step 1) with an anionic waterborne polyurethane emulsion;
3) and (3) carrying out ultrasonic treatment on the carboxyl nano-cellulose dispersion liquid obtained in the step 2) and the anionic waterborne polyurethane mixed emulsion to obtain the stable carboxyl nano-cellulose modified anionic waterborne polyurethane emulsion.
Further, the method for preparing the carboxyl nanocellulose dispersion in step 1) is as follows:
1.1 weighing 0.5-5 parts of microcrystalline cellulose, 50-300 parts by weight and 10 wt% sodium persulfate solution, and uniformly mixing;
1.2, placing the mixed solution obtained in the step 1.1 in a water bath, and carrying out stirring and ultrasonic treatment at the temperature of 30-70 ℃, wherein the ultrasonic power is controlled to be 800-1000W, and the ultrasonic treatment time is 2-3 h;
1.3 adding 500-5000 g of deionized water into the mixed solution after the ultrasonic treatment in the step 1.2 to stop the reaction to obtain milky white suspension;
1.4, performing high-speed centrifugation on the milky white suspension obtained in the step 1.3, adding deionized water, repeatedly performing centrifugal washing to be neutral, and obtaining a semitransparent to milky white carboxyl nano cellulose colloidal solution with the mass fraction of 3-5 wt%, wherein the speed of the high-speed centrifuge is 9000-10000 r/min, and the centrifugation time is not less than 10 min.
Further, the anionic aqueous polyurethane emulsion adopted in the step 2) is a carboxylic acid type aqueous polyurethane emulsion or a sulfonic acid type aqueous polyurethane emulsion with the mass fraction of 30 wt%.
Further, in the step 2), adding the anionic waterborne polyurethane emulsion into the carboxyl nano-cellulose dispersion liquid prepared in the step 1) and uniformly mixing to obtain a mixed liquid, wherein the carboxyl nano-cellulose and the anionic waterborne polyurethane in the mixed liquid areIn a mass ratio of
Further, carrying out ultrasonic treatment on the mixed emulsion obtained in the step 3), wherein the ultrasonic time is 1-2 h, the ultrasonic power is 800-1000W, and the ultrasonic temperature is not higher than 50 ℃.
Compared with the prior art, the invention has the advantages that:
1. the invention has the advantages of simple preparation process and easy industrial production;
2. according to the invention, the carboxyl nanocellulose is added into the anionic waterborne polyurethane, so that the mechanical property, the water resistance and the like of the polyurethane can be further improved;
3. the carboxyl nano-cellulose/modified anion aqueous polyurethane emulsion prepared by the preparation method disclosed by the invention is applied to the fields of adhesives and the like, and the hardness and the mechanical property of the aqueous polyurethane film can be obviously improved.
Detailed Description
The invention provides a method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose, which comprises the following steps:
1) oxidizing microcrystalline cellulose with sodium persulfate to prepare carboxyl nanocellulose to form a carboxyl nanocellulose dispersion, wherein the method for preparing the carboxyl nanocellulose dispersion comprises the following steps:
weighing 0.5-5 parts by weight of microcrystalline cellulose, 50-300 parts by weight of sodium persulfate solution with the concentration of 10 wt%, and uniformly mixing; placing the mixed solution in a water bath, and carrying out stirring and ultrasonic treatment at the temperature of 30-70 ℃, wherein the ultrasonic power is controlled to be 600-1500W, and the ultrasonic treatment time is 2-8 h; adding 500-5000 g of deionized water into the mixed solution after ultrasonic treatment to stop reaction to obtain milky white suspension; carrying out high-speed centrifugation on the milky suspension, adding deionized water, repeatedly centrifuging and washing to be neutral, and obtaining a semitransparent to milky carboxyl nano cellulose colloidal solution with the mass fraction of 3-5 wt%, wherein the speed of a high-speed centrifuge is 9000-10000 r/min, and the centrifugation time is not less than 10 min;
2) mixing the carboxyl nano-cellulose dispersion liquid obtained in the step 1) with an anionic waterborne polyurethane emulsion to obtain the carboxyl nano-cellulose and anionic waterborne polyurethane with the mass ratio of
Wherein the anionic waterborne polyurethane emulsion is a carboxylic acid type waterborne polyurethane emulsion or a sulfonic acid type waterborne polyurethane emulsion with the mass fraction of 30 wt%, and can be directly purchased in the market;
3) and (3) carrying out ultrasonic treatment on the carboxyl nano cellulose dispersion liquid obtained in the step 2) and the anionic waterborne polyurethane mixed emulsion for 1-2 h, wherein the ultrasonic power is 800-1000W, and the ultrasonic temperature is not higher than 50 ℃, so as to obtain the stable carboxyl nano cellulose modified anionic waterborne polyurethane emulsion.
According to the invention, the carboxyl nano-cellulose dispersion liquid and the anionic waterborne polyurethane are mixed, the carboxyl nano-cellulose is used for modifying the anionic waterborne polyurethane emulsion, the carboxyl nano-cellulose surface contains carboxyl anions, the waterborne polyurethane emulsion is dispersed by adopting anions (carboxylic acid type or sulfonic acid type), and both the carboxyl nano-cellulose and the anionic waterborne polyurethane contain anions, so that the compatibility is enhanced, the interface effect between the nano-cellulose and the polyurethane can be effectively reduced, and the nano-cellulose and the polyurethane can be better dispersed in the polymer.
The carboxyl nano-cellulose modified anionic waterborne polyurethane emulsion is used as an adhesive, and the bonding strength is obviously increased. Specifically, a universal tester is used for testing the peel strength: firstly, cutting the artificial leather into strips of 10 multiplied by 2.5cm, then uniformly coating the modified polyurethane emulsion on the half area of one artificial leather, pasting the other artificial leather, attaching and pressing, removing the redundant polyurethane emulsion, taking out after drying in an oven at 80 ℃ for 30min, pressing the dried artificial leather below a heavy object, and naturally cooling to room temperature to test the peeling strength.
The peel strength is divided into initial adhesive strength and final adhesive strength, the dried simulated leather is cooled to room temperature and immediately subjected to peel strength test to obtain the initial adhesive strength, and the simulated leather to be tested is placed at room temperature for 72 hours and then subjected to peel strength to obtain the final adhesive strength.
For a better understanding of the present invention, reference is made to the following examples, in which some of the preparation conditions are set forth as typical and not as limitations of the present invention.
Example 1
1) 0.5g of microcrystalline cellulose (MCC) and 50g of sodium persulfate solution with the mass fraction of 10 wt% are taken and mixed uniformly;
placing the mixed solution in a water bath, stirring and carrying out ultrasonic treatment at the temperature of 60 ℃, wherein the ultrasonic power is 800W, the ultrasonic time is 2.5h, and the ultrasonic temperature is not higher than 70 ℃;
adding 500g of deionized water to stop the reaction to obtain milky white suspension;
centrifuging the milky white suspension at 9000r/min for 10min at high speed, discarding supernatant, adding appropriate amount of deionized water, mixing, centrifuging again, repeating for 5 times, washing the solution to neutrality, and collecting semitransparent carboxyl nanocellulose colloidal solution at the bottom of the centrifuge tube;
taking a small amount of carboxyl nano cellulose colloidal solution, and calculating the mass fraction of the carboxyl nano cellulose colloidal solution to be 4.5 wt% by adopting a drying method;
2) stirring and mixing 100g of sulfonic acid type aqueous polyurethane emulsion with the solid content of 30% and 3.3g of carboxyl nano cellulose colloidal solution prepared in the step 1), wherein the stirring speed is 200r/min, and stirring for 10 min;
3) performing ultrasonic treatment, wherein the temperature is controlled to be about 45 ℃, the ultrasonic time is 1h, and the ultrasonic power is 800W, so as to obtain the carboxyl nanocellulose modified anionic waterborne polyurethane emulsion of the embodiment 1;
example 1 carboxyl nanocellulose modified anionic aqueous polyurethane emulsion
Example 2
1) Uniformly mixing 5g of microcrystalline cellulose (MCC) and 500g of sodium persulfate solution with the mass fraction of 10 wt%;
placing in a water bath, stirring and performing ultrasonic treatment at 65 ℃, wherein the ultrasonic time is 3h, the ultrasonic power is 1000W, and the ultrasonic temperature is not higher than 70 ℃;
then 5000g of deionized water is added to stop the reaction, and milky white suspension is obtained;
centrifuging the milky white suspension at a centrifugation speed of 10000r/min at a high speed for 10min, removing supernatant, adding a proper amount of deionized water, uniformly mixing, centrifuging again, repeatedly washing the solution for 7 times until the solution is neutral, taking a milky white carboxyl nano cellulose colloidal solution at the bottom of a centrifuge tube, and taking a small amount of the carboxyl nano cellulose colloidal solution to calculate the solid content of the milky white carboxyl nano cellulose colloidal solution by adopting a drying method to obtain 5 wt%;
2) stirring and mixing 200g of sulfonic acid type aqueous polyurethane emulsion with the solid content of 30% and 60g of carboxyl nano cellulose colloidal solution prepared in the step 1), wherein the stirring speed is 200r/min, and stirring for 10 min;
3) and then carrying out ultrasonic treatment, wherein the temperature is controlled to be about 40 ℃, the ultrasonic time is 2 hours, and the ultrasonic power is 1000W, so as to obtain the carboxyl nanocellulose modified anionic waterborne polyurethane emulsion in the embodiment 2.
Example 2 carboxyl nanocellulose modified anionic waterborne polyurethane emulsion
Example 3
1) 3g of microcrystalline cellulose (MCC) and 300g of sodium persulfate solution with the mass fraction of 10 wt% are taken and mixed uniformly;
placing in a water bath, stirring and performing ultrasonic treatment at 55 ℃, wherein the ultrasonic time is 2h, the ultrasonic power is 800W, and the ultrasonic temperature is not higher than 70 ℃;
adding 300g of deionized water to stop the reaction to obtain milky white suspension;
centrifuging the milky white suspension at a centrifugal speed of 9000r/min at a high speed for 10min, removing the supernatant, adding a proper amount of deionized water, uniformly mixing, centrifuging again, washing the solution to be neutral after repeating for 5 times, wherein the bottom of a centrifugal tube is a semitransparent carboxyl nano cellulose colloidal solution, and taking a small amount of the carboxyl nano cellulose colloidal solution to calculate the solid content of the carboxyl nano cellulose colloidal solution to be 3 wt% by adopting a drying method;
2) 80g of carboxylic acid type aqueous polyurethane emulsion with the solid content of 30 percent is taken to be stirred and mixed with 20g of carboxyl nano cellulose colloidal solution prepared in the step 1), the stirring speed is 200r/min, and the stirring is carried out for 10 min;
3) and then carrying out ultrasonic treatment at the ultrasonic temperature of 50 ℃, for 1.4h and with the ultrasonic power of 850W to obtain the carboxyl nanocellulose modified anionic waterborne polyurethane emulsion of the embodiment 3.
Example 3 carboxyl nanocellulose modified anionic waterborne polyurethane emulsion
The modified carboxyl nanocellulose-modified anionic aqueous polyurethane emulsions obtained in examples 1 to 3, and the existing sulfonic acid-type aqueous polyurethane emulsions and carboxylic acid-type aqueous polyurethane emulsions that were not modified with carboxyl nanocellulose were used as adhesives:
the final bond peel strength of the product of example 1 was 165N;
final bond peel strength 152N for the product of example 2;
the sulfonic acid type aqueous polyurethane emulsion which is not modified by carboxyl nano-cellulose is independently used as an adhesive, and the final adhesion peel strength is 144N;
final bond peel strength 185N for the product of example 3;
the carboxylic acid type aqueous polyurethane emulsion which is not modified by carboxyl nano-cellulose is independently used as an adhesive, and the final adhesive peel strength is 159N.
The aqueous polyurethane emulsion obtained by the method for modifying the anionic aqueous polyurethane emulsion by using the carboxyl nanocellulose has good mechanical property, water resistance and thermal stability.
The modified waterborne polyurethane emulsion prepared by the method for modifying the anionic waterborne polyurethane emulsion by using the carboxyl nanocellulose is applied to the adhesive for shoes, and the mechanical property, the water resistance, the thermal stability and the like of the adhesive can be further improved.
The method for modifying the anionic waterborne polyurethane emulsion by the carboxyl nanocellulose has the characteristics of simple process, easiness in operation and the like, is easy to realize large-scale industrial production, and has a large potential market.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
1. The method for modifying the anionic waterborne polyurethane emulsion by the carboxyl nanocellulose is characterized by comprising the following steps of:
1) oxidizing microcrystalline cellulose by using sodium persulfate to prepare carboxyl nano-cellulose to form carboxyl nano-cellulose dispersion liquid;
2) mixing the carboxyl nano cellulose dispersion liquid obtained in the step 1) with an anionic waterborne polyurethane emulsion;
3) and (3) carrying out ultrasonic treatment on the carboxyl nano-cellulose dispersion liquid obtained in the step 2) and the anionic waterborne polyurethane mixed emulsion to obtain the stable carboxyl nano-cellulose modified anionic waterborne polyurethane emulsion.
2. The method for modifying the anionic aqueous polyurethane emulsion according to claim 1, wherein the method for preparing the carboxyl nanocellulose dispersion in step 1) is as follows:
1.1 weighing 0.5-5 parts of microcrystalline cellulose, 50-300 parts by weight and 10 wt% sodium persulfate solution, and uniformly mixing;
1.2, placing the mixed solution obtained in the step 1.1 in a water bath, and carrying out stirring and ultrasonic treatment at the temperature of 30-70 ℃, wherein the ultrasonic power is controlled to be 800-1000W, and the ultrasonic treatment time is 2-3 h;
1.3 adding 500-5000 g of deionized water into the mixed solution after the ultrasonic treatment in the step 1.2 to stop the reaction to obtain milky white suspension;
1.4, performing high-speed centrifugation on the milky white suspension obtained in the step 1.3, adding deionized water, repeatedly performing centrifugal washing to be neutral, and obtaining a semitransparent to milky white carboxyl nano cellulose colloidal solution with the mass fraction of 3-5 wt%, wherein the speed of the high-speed centrifuge is 9000-10000 r/min, and the centrifugation time is not less than 10 min.
3. The method of carboxyl nanocellulose modification of anionic aqueous polyurethane emulsion as claimed in claim 2, characterized in that: the anionic waterborne polyurethane emulsion adopted in the step 2) is a carboxylic acid type waterborne polyurethane emulsion or a sulfonic acid type waterborne polyurethane emulsion with the mass fraction of 30 wt%.
4. The method of claim 3 for modifying an anionic aqueous polyurethane emulsion with carboxyl nanocellulose, wherein: in the step 2), adding the anionic waterborne polyurethane emulsion into the carboxyl nano-cellulose dispersion liquid prepared in the step 1) and uniformly mixing, wherein the mass ratio of the carboxyl nano-cellulose to the anionic waterborne polyurethane in the obtained mixed liquid is
5. The method of claim 4 for modifying an anionic aqueous polyurethane emulsion with carboxyl nanocellulose, wherein the method comprises the following steps: carrying out ultrasonic treatment on the mixed emulsion obtained in the step 3), wherein the ultrasonic time is 1-2 h, the ultrasonic power is 800-1000W, and the ultrasonic temperature is not higher than 50 ℃.
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