CN105713519B - The method of the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension - Google Patents

Abstract

A method for modifying waterborne wood coatings with two-dimensional graphene oxide hybridized zero-dimensional inorganic nanoparticles. The invention relates to a modification method of water-based wood paint. The purpose of the invention is to solve the problem of poor mechanical properties of the modified water-based wood coating caused by the poor dispersion of the existing zero-dimensional inorganic nanoparticles and two-dimensional reduced graphene in the water-based wood coating. Methods: 1. Preparation of graphene oxide aqueous dispersion; 2. Hybrid compounding of graphene oxide and inorganic nanoparticles; 3. Compounding of nanomaterials and aqueous resin emulsion. The present invention uses two-dimensional graphene oxide with high specific surface area and good water dispersibility as a carrier, and in-situ doping composite nano-SiO ₂ , Fe ₃ O ₄ , Al ₂ O ₃ , TiO ₂ , ZnO, CeO ₂ and other zero-dimensional Inorganic nanoparticles can synergistically improve the comprehensive performance of water-based wood coatings through the method of two-phase in-situ hybridization, so as to broaden the application range of water-based wood coatings and increase the added value of wood products.

Description

Two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles modified waterborne wood coatings method

technical field

The invention relates to a modification method of water-based wood paint.

Background technique

Wood has natural defects such as easy to absorb water, swell and deform, susceptible to fungal decay, susceptible to ultraviolet light aging, and easy to burn and degrade. Therefore, wood coatings are often painted on the surface of wood to improve the above defects. However, with the strengthening of people's awareness of environmental protection, the application of organic oil-soluble coatings with high VOC emissions has become more and more restricted, while environmentally friendly water-based coatings with low VOC emissions have become more and more popular and become the mainstream trend in the development of wood coatings. However, the scratch resistance, abrasion resistance, hardness, impact resistance and other mechanical properties of water-based wood coatings, as well as UV aging resistance are generally inferior to oil-based coatings with mature technology, so it is necessary to improve their performance.

In recent years, patents on the modification of waterborne wood coatings using nanomaterials have been reported. As described in the invention patent with application number 201210480069.X, the use of zero-dimensional nano-TiO ₂ , Al ₂ O ₃ , SiO ₂ , and Ag composite water-based resin emulsion makes water-based wood coatings have antibacterial properties, but direct doping of nanoparticles is easy to agglomerate , Poor interfacial compatibility with the matrix resin and other problems such as phase separation, so the mechanical strength of the water-based coating cannot be effectively enhanced. At the same time, the introduction of Ag will cause the water-based wood coating to have obvious color difference, reducing the light transmittance and gloss of the coating. The invention patent with the application number 201380049182.5 reports the preparation method of adding one-dimensional nanocellulose crystals and surfactants to water-based coatings, but only the addition of nanocellulose can affect the scratch resistance, abrasion resistance and UV aging resistance of the coating. Improvement has no positive effect. The invention patent with the application number 201410006256.3 reported a method for preparing superhydrophobic wood coatings by using one-dimensional nanocellulose and zero-dimensional nano-silica sol combined with water-dispersed resin, but the nano-cellulose loaded nano-silica was superhydrophobic first. Modification, so that the polarity difference between it and the water-dispersed resin is huge, the affinity between the two phases is poor, and the interface compatibility is poor. The superhydrophobic modified nanomaterials are easy to agglomerate, resulting in poor improvement or even decline in the mechanical properties of the coating. . The invention patent with application number 201510248010.1 reports a method of adding graphene to water-based polyurethane acrylate to prepare wood coatings with high light resistance, and the invention patent with application number 201510289998.6 reports a method for preparing graphene/water-based polyurethane composite materials , the invention patent with the application number 201410388577.4 reports a preparation method for graphene to improve the light resistance of water-based paints and adhesives, but these patents use the graphene obtained through the reduction step to modify the water-based paint, and there is graphite Due to the complex preparation/modification process of alkene, poor dispersion in coatings, and weak bonding force with the resin matrix interface, the improvement of the mechanical properties of water-based coatings is limited.

In short, the zero-dimensional inorganic nanoparticles modified water-based wood coatings stated in the above-mentioned published patents have the problems of poor dispersion of nanoparticles, poor mechanical properties of the coating, and poor improvement of light transmittance; one-dimensional organic nanocellulose is mostly rod-shaped The nano-cellulose crystals with low aspect ratio have limited improvement on the impact toughness, scratch resistance and wear resistance of the coating, and cannot improve the weather resistance of the coating; while one-dimensional nano-cellulose and zero-dimensional SiO ₂ , TiO ₂ and other composites, the method used also has the smaller specific surface area of one-dimensional nanocellulose than that of two-dimensional nanomaterials, its poor affinity with the polymer matrix, and poor dispersion in the polymer matrix, resulting in insufficient improvement in the mechanical properties of the coating. good question. Although the use of two-dimensional graphene can improve water-based coatings to a certain extent, the preparation process of graphene obtained by the reduction method is complicated, the dispersion is poor, the mechanical properties of water-based coatings are not improved well, and there are no additional functions such as sterilization and electromagnetic shielding.

Contents of the invention

The purpose of the present invention is to provide a two-dimensional graphene oxide to solve the problem of poor mechanical properties of the modified water-based wood coating caused by the poor dispersion of the existing zero-dimensional inorganic nanoparticles and two-dimensional reduced graphene in the water-based wood coating. A method for modifying waterborne wood coatings by hybridizing zero-dimensional inorganic nanoparticles.

The method of a kind of two-dimensional graphene oxide hybridization zero-dimensional inorganic nanoparticles modified water-based wood coating of the present invention is carried out as follows:

1. Preparation of graphene oxide aqueous dispersion: ①Put graphite powder into a beaker, add concentrated sulfuric acid at a rate of 20g/min to 30g/min in an ice-water bath, then add sodium nitrate, stir for 4min to 6min, and then continue Add potassium permanganate under an ice-water bath, stir at a speed of 900r/min~1100r/min for 25min~35min, then raise the temperature to 30℃~40℃ at a speed of 3℃/min~4℃/min, and Stir and react at 30°C to 40°C for 1.5h to 2.5h to obtain the mixed solution A;

The ratio of the quality of described graphite powder to the volume of concentrated sulfuric acid is 1g: (25～35) mL; The mass ratio of described graphite powder and sodium nitrate is 1: (0.4～0.6); Described graphite powder and The mass ratio of potassium permanganate is 1: (6-8);

② Add distilled water Ⅰ to the mixture A obtained in step ① at a speed of 50g/min～60g/min, stir at a speed of 900r/min～1100r/min for 4min～6min, and then continue to mix at a speed of 50g/min～60g/min Add distilled water II at a high speed, stir at a speed of 900r/min~1100r/min for 9min~11min, then continue to add distilled water III at a speed of 50g/min~60g/min, and then increase the temperature at a rate of 3℃/min~4℃/min Increase the speed to 92-98°C, stir at a speed of 900r/min-1100r/min for 25min-35min, then add hydrogen peroxide solution with a mass concentration of 25%-35% until there are no bubbles and the color of the solution turns golden yellow. Obtain mixed solution B;

The ratio of the volume of the distilled water I to the mass of the graphite powder in step 1. is (4-6) mL:1g, and the volume ratio of the distilled water I to the distilled water II is 1: (1.5-2.5), and the The volume ratio of distilled water I to distilled water III is 1: (15-25); the volume ratio of distilled water I to hydrogen peroxide solution with a mass concentration of 25% to 35% is 1: (5 to 20);

③Let the mixed solution B obtained in step ② stand for 10h～14h, layer up, remove the supernatant, and then wash with dilute hydrochloric acid with a mass concentration of 8%～12% for 3～5 times to remove sulfate radicals in the solution ions, and then washed with deionized water several times until the solution was detected to contain no chloride ions with silver nitrate solution, and then the pH value was adjusted to 4-5 to obtain a suspension;

④Centrifuge the suspension obtained in step ③ for 3 times at a speed of 7000r/min~9000r/min, each time for 10min~15min, and then centrifuge 3 times at a speed of 2500r/min~3500r/min , 10min to 15min each time, after centrifugation, place the obtained precipitate in a dialysis bag, and then stir and dialyze it in deionized water at a speed of 300r/min to 500r/min for one week to obtain graphite oxide;

⑤Add the graphite oxide obtained in step ④ into deionized water, use an ultrasonic cell pulverizer to sonicate for 15min~25min at a power of 750W~850W, and then stir at a high speed for 10min at a speed of 13000r/min~15000r/min ~12min to obtain a uniformly dispersed graphene oxide aqueous dispersion;

The ratio of the mass of graphite oxide obtained in step ④ described in step ⑤ to the volume of deionized water is (0.6～0.8) g: 200mL;

2. Hybrid compounding of graphene oxide and inorganic nanoparticles: add zero-dimensional inorganic nanoparticles to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1, and ultrasonicate for 30 minutes to 240 minutes at a power of 300W to 1000W , to obtain the hybrid compound solution;

The mass ratio of the zero-dimensional inorganic nanoparticles to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is (10-50):100;

3. Compounding of nanomaterials and water-based resin emulsion: ① Add cationic surfactant to the hybrid compound liquid obtained in step 2, and ultrasonicate for 30 min to 240 min at a power of 300W ~ 1000W to obtain a compound liquid; The liquid is rotary steamed until 50%-80% of the moisture in the composite liquid is removed, and then the composite liquid is added to the water-based wood coating, and then ultrasonicated for 30min-240min under the condition of a power of 300W-1000W; ③ at a speed of 14000r/ Under the condition of min～16000r/min, stir at a high speed for 25min～35min to obtain a water-based wood coating modified by two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles;

The mass ratio of the quality of the cationic surfactant to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is (0.5-1): 100; the graphite oxide in the composite liquid after the rotary evaporation is The mass ratio of the mass of alkene to the solid content of the water-based wood coating is (0.2-0.8): 100, wherein the solid content of the water-based wood coating is 30%.

Beneficial effects of the present invention:

The present invention proposes a two-dimensional graphene oxide with high specific surface area and good water dispersibility as a carrier, in-situ doped composite nano-SiO ₂ , Fe ₃ O ₄ , Al ₂ O ₃ , TiO ₂ , ZnO, CeO ₂ and other zero-dimensional inorganic nanoparticles, synergistically improve the mechanical properties such as scratch resistance, wear resistance, hardness, impact toughness and UV aging resistance of water-based wood coatings through the method of two-phase in-situ hybridization, and even endow them with sterilization and purification The function of air and electromagnetic shielding can significantly improve the service life of water-based wood coatings, increase the function of water-based wood coatings, broaden the application range of water-based wood coatings, and increase the added value of wood products.

Description of drawings

Fig. 1 is the TEM figure of the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion that test one step one obtains;

Fig. 2 is the AFM figure of graphene oxide in the uniformly dispersed graphene oxide water dispersion liquid that test one step one obtains;

Fig. 3 is the SEM figure of the water-based wood coating modified by the two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles obtained in test one;

Fig. 4 is the SEM image of the two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles modified waterborne wood coating obtained in the second experiment.

detailed description

Specific embodiment one: the method for the two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle modified water-based wood coating of the present embodiment is characterized in that the method is carried out in the following steps:

1. Preparation of graphene oxide aqueous dispersion: ①Put graphite powder into a beaker, add concentrated sulfuric acid at a rate of 20g/min to 30g/min in an ice-water bath, then add sodium nitrate, stir for 4min to 6min, and then continue Add potassium permanganate under an ice-water bath, stir at a speed of 900r/min~1100r/min for 25min~35min, then raise the temperature to 30℃~40℃ at a speed of 3℃/min~4℃/min, and Stir and react at 30°C to 40°C for 1.5h to 2.5h to obtain the mixed solution A;

The ratio of the quality of described graphite powder to the volume of concentrated sulfuric acid is 1g: (25～35) mL; The mass ratio of described graphite powder and sodium nitrate is 1: (0.4～0.6); Described graphite powder and The mass ratio of potassium permanganate is 1: (6-8);

② Add distilled water Ⅰ to the mixture A obtained in step ① at a speed of 50g/min～60g/min, stir at a speed of 900r/min～1100r/min for 4min～6min, and then continue to mix at a speed of 50g/min～60g/min Add distilled water II at a high speed, stir at a speed of 900r/min~1100r/min for 9min~11min, then continue to add distilled water III at a speed of 50g/min~60g/min, and then increase the temperature at a rate of 3℃/min~4℃/min Increase the speed to 92-98°C, stir at a speed of 900r/min-1100r/min for 25min-35min, then add hydrogen peroxide solution with a mass concentration of 25%-35% until there are no bubbles and the color of the solution turns golden yellow. Obtain mixed solution B;

The ratio of the volume of the distilled water I to the mass of the graphite powder in step 1. is (4-6) mL:1g, and the volume ratio of the distilled water I to the distilled water II is 1: (1.5-2.5), and the The volume ratio of distilled water I to distilled water III is 1: (15-25); the volume ratio of distilled water I to hydrogen peroxide solution with a mass concentration of 25% to 35% is 1: (5 to 20);

③Let the mixed solution B obtained in step ② stand for 10h～14h, layer up, remove the supernatant, and then wash with dilute hydrochloric acid with a mass concentration of 8%～12% for 3～5 times to remove sulfate radicals in the solution ions, and then washed with deionized water several times until the solution was detected to contain no chloride ions with silver nitrate solution, and then the pH value was adjusted to 4-5 to obtain a suspension;

④Centrifuge the suspension obtained in step ③ for 3 times at a speed of 7000r/min~9000r/min, each time for 10min~15min, and then centrifuge 3 times at a speed of 2500r/min~3500r/min , 10min to 15min each time, after centrifugation, place the obtained precipitate in a dialysis bag, and then stir and dialyze it in deionized water at a speed of 300r/min to 500r/min for one week to obtain graphite oxide;

⑤Add the graphite oxide obtained in step ④ into deionized water, use an ultrasonic cell pulverizer to sonicate for 15min~25min at a power of 750W~850W, and then stir at a high speed for 10min at a speed of 13000r/min~15000r/min ~12min to obtain a uniformly dispersed graphene oxide aqueous dispersion;

The ratio of the mass of graphite oxide obtained in step ④ described in step ⑤ to the volume of deionized water is (0.6～0.8) g: 200mL;

2. Hybrid compounding of graphene oxide and inorganic nanoparticles: add zero-dimensional inorganic nanoparticles to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1, and ultrasonicate for 30 minutes to 240 minutes at a power of 300W to 1000W , to obtain the hybrid compound solution;

The mass ratio of the zero-dimensional inorganic nanoparticles to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is (10-50):100;

3. Compounding of nanomaterials and water-based resin emulsion: ① Add cationic surfactant to the hybrid compound liquid obtained in step 2, and ultrasonicate for 30 min to 240 min at a power of 300W ~ 1000W to obtain a compound liquid; The liquid is rotary steamed until 50%-80% of the moisture in the composite liquid is removed, and then the composite liquid is added to the water-based wood coating, and then ultrasonicated for 30min-240min under the condition of a power of 300W-1000W; ③ at a speed of 14000r/ Under the condition of min～16000r/min, stir at a high speed for 25min～35min to obtain a water-based wood coating modified by two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles;

The mass ratio of the quality of the cationic surfactant to the uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is (0.5-1): 100; the graphite oxide in the composite liquid after the rotary evaporation is The mass ratio of the mass of alkene to the solid content of the water-based wood coating is (0.2-0.8): 100, wherein the solid content of the water-based wood coating is 30%.

Specific embodiment two: the difference between this embodiment and specific embodiment one is: the ratio of the quality of the graphite powder described in step one and the volume of concentrated sulfuric acid is 1g: 30mL; The mass ratio of described graphite powder and sodium nitrate 1:0.5; the mass ratio of graphite powder to potassium permanganate is 1:7. Other steps and parameters are the same as those in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the zero-dimensional inorganic nanoparticles described in Step 2 are SiO ₂ , Fe ₃ O ₄ , Al ₂ O ₃ , TiO ₂ , ZnO and CeO ₂ any one or a mixture of several. Other steps and parameters are the same as those in Embodiment 1 or 2.

Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that: the particle size of the zero-dimensional inorganic nanoparticles described in step 2 is 10 nm to 30 nm. Other steps and parameters are the same as those in the first to third specific embodiments.

Specific embodiment five: the difference between this embodiment and one of specific embodiments one to four is: the zero-dimensional inorganic nanoparticles described in step two and the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion obtained in step one The mass ratio is 20:100. Other steps and parameters are the same as in one of the specific embodiments 1 to 4.

Specific embodiment six: this embodiment is different from one of specific embodiments one to five: the cationic surfactant described in step 3 is hexadecyl trimethyl ammonium bromide, octadecyl trimethyl bromide Any one or a combination of ammonium chloride, cetyltrimethylammonium chloride and octadecyltrimethylammonium chloride. Other steps and parameters are the same as one of the specific embodiments 1 to 5.

Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that the water-based wood coating described in step 3 is water-based polyurethane acrylic wood coating or water-based acrylic wood coating. Other steps and parameters are the same as one of the specific embodiments 1 to 6.

Embodiment 8: This embodiment is different from one of Embodiments 1 to 7 in that: the water-based polyurethane acrylic wood coating is composed of water-based polyurethane acrylic resin, deionized water and curing agent, and the water-based polyurethane acrylic wood coating The solid content is 30%, and the quality of the curing agent is 0.5% to 1% of the solid content of the waterborne polyurethane acrylic resin. The curing agent is an amino resin low-temperature self-crosslinking curing agent or an acyl phosphorus oxide UV light curing agent. Other steps and parameters are the same as one of the specific embodiments 1 to 7.

Specific embodiment nine: this embodiment is different from one of specific embodiments one to eight in that: the water-based acrylic wood coating is composed of water-based acrylic resin, deionized water and curing agent, and the solid content of the water-based acrylic wood coating The mass of the curing agent is 0.5% to 1% of the solid content of the water-based acrylic resin, and the curing agent is an amino resin low-temperature self-crosslinking curing agent or an acyl phosphorus oxide ultraviolet curing agent. Other steps and parameters are the same as one of the specific embodiments 1 to 8.

Specific embodiment ten: this embodiment is different from one of specific embodiments one to nine: the ratio of the quality of graphene oxide and the solid content of water-based wood coatings in the composite liquid after rotary steaming described in step 3 is (0.53～0.67 ): 100. Other steps and parameters are the same as one of the specific implementation modes 1 to 9.

Test one: the method of a kind of two-dimensional graphene oxide hybridization zero-dimensional inorganic nanoparticles modified waterborne wood coating of this test is carried out according to the following steps:

1. Preparation of graphene oxide aqueous dispersion: ①Put 1g of graphite powder into a beaker, add 30mL of concentrated sulfuric acid at a rate of 30g/min under an ice-water bath, then add 0.5g of sodium nitrate, stir for 5min, and then continue to dissolve in ice water. Add 7g of potassium permanganate in a water bath, stir at a speed of 1000r/min for 30min, then raise the temperature to 35°C at a speed of 3°C/min, and stir and react at a temperature of 35°C for 2h to obtain a mixed solution A;② Add 5mL of distilled water I to the mixture A obtained in step ① at a speed of 60g/min, stir for 5min at a speed of 1000r/min, then continue to add 10mL of distilled water II at a speed of 60g/min, and stir for 10min at a speed of 1000r/min , and then continue to add 100mL of distilled water III at a speed of 60g/min, then raise the temperature to 95°C at a speed of 4°C/min, stir at a speed of 1000r/min for 30min, and then add 50mL of hydrogen peroxide with a mass concentration of 30% Solution until no bubbles occur and the color of the solution turns golden yellow to obtain the mixed solution B; ③ After the mixed solution B obtained in step ② is allowed to stand for 12 hours, separate layers, remove the supernatant, and then use dilute solution with a mass concentration of 10% Wash 4 times with hydrochloric acid to remove sulfate ions in the solution, then wash repeatedly with deionized water until no chloride ions are detected in the solution with silver nitrate solution, then adjust the pH value to 4.5 to obtain a suspension; ④ the steps ③ The obtained suspension was first centrifuged 3 times under the condition of rotating speed of 8000r/min, 15min each time, and then centrifuged 3 times under the condition of rotating speed of 3000r/min, 15min each time. Put it in a dialysis bag, and then stir and dialyze it in deionized water at a speed of 300r/min for one week to obtain graphite oxide; Ultrasound for 20 minutes under the condition of power of 800W, and then high-speed stirring for 10 minutes under the condition of rotating speed of 14000r/min, to obtain a uniformly dispersed graphene oxide aqueous dispersion;

2. Hybrid compounding of graphene oxide and inorganic nanoparticles: 0.06g nanometer _SiO2 particles and 0.06g nanometer ZnO particles are added to 200mL of uniformly dispersed graphene oxide aqueous dispersion obtained in step 1, and the power is 800W Ultrasound for 30 minutes under the same conditions to obtain a hybrid compound solution;

The mass ratio of the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion obtained by the zero-dimensional inorganic nanoparticles and step one is 20:100; the particle diameter of the nano- _SiO2 particles is 30nm; the The particle size of nano ZnO particles is 10nm;

3. Compounding of nanomaterials and water-based resin emulsion: ①Add 0.006g of hexadecyltrimethylammonium bromide to 200mL of the hybrid compound liquid obtained in step 2, and ultrasonicate for 30min at a power of 800W to obtain a compound ② Rotate the composite solution until 80% of the moisture in the composite solution is removed, then add 40mL of the composite solution into 300mL of water-based wood coating, and then ultrasonicate for 30min at a power of 800W; ③ At a speed of 15000r/ Min under the condition of high-speed stirring for 30 minutes, to obtain two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles modified water-based wood coatings;

The mass ratio of the quality of the cationic surfactant to the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion obtained in step one is 1:100; the mass ratio of the graphene oxide in the composite liquid after the rotary evaporation to The ratio of the solid content of the water-based wood coating is 0.67:100, wherein the solid content of the water-based wood coating is 30%.

Described water-based wood coating is water-based polyurethane acrylic wood coating; wherein said water-based polyurethane acrylic wood coating is composed of water-based polyurethane acrylic resin, deionized water and curing agent, and the solid content of said water-based polyurethane acrylic wood coating is 30% , the quality of the curing agent is 1% of the solid content of the water-based polyurethane acrylic resin, and the curing agent is an amino resin low-temperature self-crosslinking curing agent.

Wherein, the water-based wood coating is purchased from Carpoly Chemical Group Co., Ltd.

(1) The uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is scanned by transmission electron microscope, and the TEM figure of graphene oxide as shown in Figure 1 is obtained. As can be seen from Figure 1, the size of graphene oxide microplates is between 0.5μm～3μm.

(2) The uniformly dispersed graphene oxide aqueous dispersion obtained in step 1 is detected by atomic force microscopy, and the AFM figure of graphene oxide as shown in Figure 2 is obtained. As can be seen from Figure 2, the thickness of graphene oxide is between About 0.55nm～1.2nm, with very high specific surface area (>500m ² /g), no precipitation.

(3) The two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle-modified water-based wood coating obtained in Test 1 is coated on the wood to form a paint film, and the surface of the paint film is detected by a scanning electron microscope, as shown in Figure 3 The SEM image of the two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle modified waterborne wood coating shown in Figure 3 shows that tens of nanometers of inorganic nanoparticles are uniformly distributed on the surface of the paint film, indicating that graphene oxide It acts as a very good dispersion carrier and effectively solves the problem that it is difficult to uniformly disperse inorganic nanoparticles in the resin matrix.

(4) The two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle modified water-based wood coating and the unmodified wood coating obtained in Test ¹ were applied to the maple surface by spraying at a spraying amount of 120g/m2 , after drying for 72 hours at a temperature of 35°C, the mechanical properties, UV aging resistance and bactericidal properties of the paint film were tested. The results showed that the hardness of the modified paint film was increased by 44.1% compared with the unmodified control paint film , the wear resistance increased by 45.5%, the scratch resistance increased by 18%, the impact toughness increased by 22.7%, the UV aging resistance time increased by 1.5 times, and the mold load rate on the surface of the paint film decreased by more than 85%, indicating that This method can effectively improve the comprehensive performance of waterborne wood coatings and endow them with bactericidal function.

Test two: the method of a kind of two-dimensional graphene oxide hybridized zero-dimensional inorganic nanoparticles modified water-based wood coating of this test is carried out according to the following steps:

1. Preparation of graphene oxide aqueous dispersion: ①Put 1g of graphite powder into a beaker, add 30mL of concentrated sulfuric acid at a rate of 25g/min under an ice-water bath, then add 0.5g of sodium nitrate, stir for 5min, and then continue to dissolve in ice water. Add 7g of potassium permanganate in a water bath, stir at a speed of 1000r/min for 30min, then raise the temperature to 35°C at a speed of 4°C/min, and stir and react at a temperature of 35°C for 2h to obtain a mixed solution A;② Add 5mL of distilled water I to the mixture A obtained in step ① at a speed of 50g/min, stir for 5min at a speed of 1000r/min, then continue to add 10mL of distilled water II at a speed of 50g/min, and stir for 10min at a speed of 1000r/min , and then continue to add 100mL of distilled water III at a speed of 50g/min, then raise the temperature to 95°C at a speed of 4°C/min, stir at a speed of 1000r/min for 30min, and then add 70mL of hydrogen peroxide with a mass concentration of 30% Solution until no bubbles are produced and the color of the solution turns golden yellow to obtain the mixed solution B; ③ After the mixed solution B obtained in step ② is allowed to stand for 12 hours, separate layers, remove the supernatant, and then use dilute solution with a mass concentration of 10% Wash 5 times with hydrochloric acid to remove sulfate ions in the solution, then wash repeatedly with deionized water until no chloride ions are detected in the solution with silver nitrate solution, then adjust the pH value to 4.5 to obtain a suspension; ④ the steps ③ The obtained suspension was first centrifuged 3 times at a rotational speed of 8000r/min, 15min each time, and then centrifuged 3 times at a rotational speed of 3000r/min, 15min each time. in deionized water, and then stirred and dialyzed in deionized water at a speed of 400r/min for one week to obtain graphite oxide; Ultrasound for 20 minutes under the condition of power of 800W, and then high-speed stirring for 10 minutes under the condition of rotating speed of 14000r/min, to obtain a uniformly dispersed graphene oxide aqueous dispersion;

2. Hybrid compounding of graphene oxide and inorganic nanoparticles: 0.1g nanometer Fe ₃ O ₄ particles and 0.1g nanometer TiO ₂ particles are added to the uniformly dispersed graphene oxide aqueous dispersion obtained in 200mL step 1. Ultrasound for 30 minutes under the condition of 800W to obtain the hybrid compound solution;

The mass ratio of the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion obtained by the zero-dimensional inorganic nanoparticles to step 1 is 25:100; the particle diameter of the nano Fe ₃ O ₄ particles is 15nm; the Described nanometer _TiO The particle diameter of particle is 10nm;

3. Compounding of nanomaterials and water-based resin emulsion: ①Add 0.004g of octadecyltrimethylammonium chloride to 200mL of the hybrid compound liquid obtained in step 2, and ultrasonicate for 30min at a power of 800W to obtain a compound ② Rotate the composite solution until 60% of the water in the composite solution is removed, then add 80mL of the compound solution into 500mL water-based wood coating, and then ultrasonicate for 30min under the condition of 800W power; ③Use 15000r/ Min under the condition of high-speed stirring for 30 minutes, to obtain two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles modified water-based wood coatings;

The mass ratio of the quality of the cationic surfactant to the graphene oxide in the uniformly dispersed graphene oxide aqueous dispersion obtained in step one is 0.5:100; the mass ratio of the graphene oxide in the composite liquid after the rotary evaporation is The ratio of the solid content of the water-based wood coating is 0.53:100, wherein the solid content of the water-based wood coating is 30%.

Described water-based wood coating is water-based polyurethane acrylic wood coating; wherein said water-based polyurethane acrylic wood coating is composed of water-based polyurethane acrylic resin, deionized water and curing agent, and the solid content of said water-based polyurethane acrylic wood coating is 30% , the quality of the curing agent is 1% of the solid content of the water-based polyurethane acrylic resin, and the curing agent is an acyl phosphorus oxide UV curing agent.

Wherein, the water-based wood coating is purchased from Carpoly Chemical Group Co., Ltd.

(5) The two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle modified water-based wood coating obtained in the second test is applied to the wood to form a paint film, and the surface of the paint film is detected by scanning electron microscopy, as shown in Figure 4 The SEM image of the two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticle modified waterborne wood coating shown in Figure 4 shows that tens of nanometers of inorganic nanoparticles are uniformly distributed on the surface of the paint film, indicating that graphene oxide It acts as a very good dispersion carrier and effectively solves the problem that it is difficult to uniformly disperse inorganic nanoparticles in the resin matrix.

(6) The two-dimensional graphene oxide hybrid zero-dimensional inorganic nanoparticles modified water-based wood coating and the unmodified wood coating obtained in the ^second test were applied to the maple surface by spraying at a spraying amount of 120g/m2 , cured at 600W/cm UV intensity for 10s and then placed at room temperature for 72 hours to test the mechanical properties, UV aging resistance and bactericidal properties of the paint film. The results showed that the hardness of the modified paint film was lower than that of the unmodified control paint The film has been improved by 35.4%, abrasion resistance by 38.2%, scratch resistance by 15%, impact toughness by 20.9%, UV aging resistance time by 1.2 times, and mold load rate on the surface of the paint film has been reduced More than 90%, the magnetic intensity can reach 46emu/g, indicating that this method can effectively improve the comprehensive performance of water-based wood coatings, and endow sterilization and electromagnetic shielding functions.

Claims (9)

1. the method for the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension, it is characterised in that the party Method is carried out according to the following steps：

First, the preparation of graphene oxide aqueous dispersions：1. graphite powder is put into beaker, under ice-water bath with 20g/min~ 30g/min speed adds the concentrated sulfuric acid, then adds sodium nitrate, stirs 4min~6min, then proceedes to add under ice-water bath Potassium permanganate, 25min~35min, then the speed with 3 DEG C/min~4 DEG C/min are stirred with 900r/min~1100r/min speed Degree is warming up to 30 DEG C~40 DEG C, and stirring reaction 1.5h~2.5h under conditions of temperature is 30 DEG C~40 DEG C, obtains mixed liquor A；

The ratio of the quality of described graphite powder and the volume of the concentrated sulfuric acid is 1g：(25~35) mL；Described graphite powder and sodium nitrate Mass ratio be 1：(0.4~0.6)；Described graphite powder and the mass ratio of potassium permanganate are 1：(6~8)；

2. in the mixed liquor A 1. obtained to step with 50g/min~60g/min speed add distilled water I, with 900r/min~ 1100r/min speed stirring 4min~6min, then proceedes to add distilled water II with 50g/min~60g/min speed, with 900r/min~1100r/min speed stirring 9min~11min, is further continued for being added with 50g/min~60g/min speed and steamed Distilled water III, temperature is then risen to 92~98 DEG C with 3 DEG C/min~4 DEG C/min speed, with 900r/min~1100r/min's Speed stirs 25min~35min, then adds hydrogenperoxide steam generator that mass concentration is 25%~35% to not effervescent and molten Liquid color becomes golden yellow, obtains mixed liquid B；

The ratio of the volume of described distilled water I and the step 1. quality of middle graphite powder is (4~6) mL:1g, described distilled water I Volume ratio with distilled water II is 1：The volume ratio of (1.5~2.5), described distilled water I and distilled water III is 1：(15~25)； The volume ratio for the hydrogenperoxide steam generator that described distilled water I is 25%~35% with mass concentration is 1：(5~20)；

3. after 2. mixed liquid B that step is obtained stands 10h~14h, layering, supernatant is removed, is then with mass concentration first 8%~12% watery hydrochloric acid washs 3~5 times, removes the sulfate ion in solution, then is repeatedly washed with deionized water to using nitre In acid silver-colored solution detection solution pH value is not then adjusted to 4~5, obtains suspension untill chloride ion-containing；

4. 3. suspension that step obtains first is centrifuged 3 times under conditions of rotating speed is 7000r/min~9000r/min, every time 10min~15min, then centrifuged 3 times, each 10min~15min under conditions of rotating speed is 2500r/min~3500r/min, Obtained sediment is placed in bag filter after centrifugal treating, then stirred in deionized water with 300r/min~500r/min speed Dialysis one week is mixed, obtains graphite oxide；

5. 4. graphite oxide that step is obtained is added in deionized water, with Ultrasonic cell smash power be 750W~ Ultrasonic 15min~25min under conditions of 850W, then rotating speed be 13000r/min~15000r/min under conditions of high-speed stirring 10min~12min is mixed, obtains finely dispersed graphene oxide aqueous dispersions；

Step 5. described in the step of the quality of graphite oxide that 4. obtains and the ratio of deionized water volume be (0.6~0.8) g： 200mL；

2nd, the hybridization compounding of graphene oxide and inorganic nano-particle：Zero dimension inorganic nano-particle is added into step 1 to obtain Finely dispersed graphene oxide aqueous dispersions in, power be 300W~1000W under conditions of ultrasonic 30min~ 240min, obtain hybridization compounding liquid；

Stone is aoxidized in the finely dispersed graphene oxide aqueous dispersions that described zero dimension inorganic nano-particle obtains with step 1 The mass ratio of black alkene is (10~50):100；

3rd, nano material and resin aqueous emulsion is compound：1. by cationic surfactant be added to step 2 obtain it is miscellaneous Change in complex liquid, ultrasonic 30min~240min under conditions of power is 300W~1000W, obtain complex liquid；2. by complex liquid Revolving is to the 50%~80% of removal complex liquid moisture, then complex liquid after revolving is added in water-borne wood coating, Ran Hou Power is ultrasonic 30min~240min under conditions of 300W~1000W；3. it is 14000r/min~16000r/min's in rotating speed Under the conditions of high-speed stirred 25min~35min, obtain the inorganic nano particle modified Waterborne wood of two dimensional oxidation graphene hydridization zero dimension Device coating；

In the finely dispersed graphene oxide aqueous dispersions that the quality of described cationic surfactant obtains with step 1 The mass ratio of graphene oxide is (0.5~1)：100；After described revolving in complex liquid graphene oxide quality and Waterborne wood The mass ratio of device coating solids is (0.2~0.8)：100, wherein the solid content of described water-borne wood coating is 30%；

Cationic surfactant described in step 3 is cetyl trimethylammonium bromide, octadecyl trimethyl bromination Any one or a few combination in ammonium, hexadecyltrimethylammonium chloride and OTAC.

2. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the ratio of the quality of the graphite powder described in step 1 and the volume of the concentrated sulfuric acid is 1g：30mL；Described stone The mass ratio of ink powder and sodium nitrate is 1：0.5；Described graphite powder and the mass ratio of potassium permanganate are 1：7.

3. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the zero dimension inorganic nano-particle described in step 2 is SiO₂、Fe₃O₄、Al₂O₃、TiO₂, ZnO and CeO₂ In any one or a few mixing.

4. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the particle diameter of the zero dimension inorganic nano-particle described in step 2 is 10nm~30nm.

5. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the finely dispersed graphite oxide that the zero dimension inorganic nano-particle described in step 2 obtains with step 1 The mass ratio of graphene oxide is 20 in alkene aqueous dispersions:100.

6. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the water-borne wood coating described in step 3 is watersoluble polyurethane acrylic acid woodwork coating or aqueous acrylamide Sour woodwork coating.

7. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 6 Method, it is characterised in that described watersoluble polyurethane acrylic acid woodwork coating is by water-soluble polyurethane acrylic resin, deionized water Formed with curing agent, the solid content of described watersoluble polyurethane acrylic acid woodwork coating is 30%, the quality of described curing agent For the 0.5%~1% of water-soluble polyurethane acrylic resin solid content, described curing agent is that amino resins class low-temperature self-crosslinking is consolidated Agent or acyl group phosphorus oxidation species ultraviolet curable agent.

8. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 6 Method, it is characterised in that described water soluble acrylic acid woodwork coating is made up of water-based acrylic resin, deionized water and curing agent, The solid content of described water soluble acrylic acid woodwork coating is 30%, and the quality of described curing agent contains admittedly for water-based acrylic resin The 0.5%~1% of amount, described curing agent is amino resins class low-temperature self-crosslinking curing agent or acyl group phosphorus oxidation species ultraviolet light Curing agent.

9. the inorganic nano particle modified water-borne wood coating of two dimensional oxidation graphene hydridization zero dimension according to claim 1 Method, it is characterised in that the quality of graphene oxide contains admittedly with water-borne wood coating in complex liquid after the revolving described in step 3 The ratio of amount is (0.53~0.67)：100.