CN112144316A - Nano-cellulose modified acrylic resin, preparation method thereof and decorative paper - Google Patents
Nano-cellulose modified acrylic resin, preparation method thereof and decorative paper Download PDFInfo
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- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
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- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
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- D21H19/00—Coated paper; Coating material
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- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Abstract
The invention relates to the technical field of composite materials, in particular to a nano-cellulose modified acrylic resin, a preparation method thereof and decorative paper, which comprise the following raw materials in parts by weight: 5-10 parts of modified nano-cellulose, 20-40 parts of acrylic resin, 1-5 parts of hydroxy cellulose, 1-3 parts of methyl allyl alcohol, 1-3 parts of bactericide, 0.1-3.0 parts of coupling agent, 0.01-1.0 part of antioxidant, 30-40 parts of solvent and 0.1-3.0 parts of filler. The modified nanocellulose adopted in the nanocellulose modified acrylic resin can be well dispersed in an acrylic resin matrix to improve the effect of two-phase interfaces, so that the prepared nanocellulose modified acrylic resin has the characteristics of good strength, elasticity and wear resistance, high curing speed, good mechanical property and chemical corrosion resistance, strong adhesive force, high temperature resistance and long service life, and the prepared decorative paper has excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nano-cellulose modified acrylic resin, a preparation method thereof and decorative paper.
Background
The impregnated decorative paper is prepared by mixing non-woven wood pulp, PE and plant fibers, and has super-strong absorption capacity and dissolution resistance. At present, with the progress of society and the improvement of living standard of people, the impregnated decorative paper is widely applied to the veneering of cupboards, wardrobes and composite floors, and the environmental protection problem and the use safety, such as moisture resistance and flame retardance, of the impregnated decorative paper are increasingly attracting attention of people. In the prior art, the prepared impregnated decorative paper has poor stability, wear resistance, oxidation resistance and other functions due to poor performance of the adopted acrylic resin adhesive, so that the service life of the impregnated decorative paper is limited, and the environmental protection and the use safety of the impregnated decorative paper need to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the nano-cellulose modified acrylic resin, wherein the adopted modified nano-cellulose can be well dispersed in an acrylic resin matrix to improve the action of a two-phase interface, so that the prepared nano-cellulose modified acrylic resin has the characteristics of good strength, elasticity, wear resistance, high curing speed, good mechanical property and chemical corrosion resistance, strong adhesive force, good ductility, high temperature resistance and long service life.
The invention also aims to provide a preparation method of the nanocellulose modified acrylic resin, which is simple to operate, convenient to control, high in production efficiency and low in production cost.
Still another object of the present invention is to provide a decorative paper having excellent antibacterial, antioxidant, weather-resistant and heat-resistant effects, thereby obtaining a decorative paper with excellent properties.
The purpose of the invention is realized by the following technical scheme: the nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
The modified nano-cellulose adopted in the invention has obvious property and effect, can be well dispersed in the acrylic resin matrix to improve the function of two-phase interface, so that the prepared nano-cellulose modified acrylic resin has the characteristics of excellent strength, elasticity, wear resistance, high curing speed, better mechanical property and chemical corrosion resistance, strong adhesive force, good ductility, high temperature resistance and long service life. The acrylic resin coating film adopted by the invention has excellent performance, good light resistance, weather resistance, heat resistance, excessive baking resistance, chemical resistance, corrosion resistance and other performances, so that the coating made of the acrylic resin has the defect of poor stability, the modified nano-cellulose is adopted to modify the acrylic resin, so that the prepared nano-cellulose modified acrylic resin has better stability, the formed coating is smooth and elastic, and has excellent functions of water resistance, pollution resistance, bacteria resistance and the like, the plasticizing temperature can be reduced to 150 ℃ compared with the plasticizing temperature of the traditional PVC paste, the wollastonite-polylactic acid porous fiber containing potassium titanate whiskers can effectively enhance the air permeability of the coating while enhancing the wear resistance of the coating, the modified nano-cellulose material has good suspension property in emulsion, the modification effect is efficient and stable, and the novel fire-resistant wallpaper prepared by the method has high safety, the device is extremely durable, economical and environment-friendly; the adopted hydroxy cellulose is taken as a stabilizer, so that the stability of the nano cellulose modified acrylic resin system is improved, and the bonding property of the system can also be improved; the added bactericide can obviously improve the antibacterial and corrosion-resistant effects of the system.
Preferably, each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
Preferably, the modified nanocellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 40-60 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 40-60 ℃, and stirring at the speed of 250-300r/min for 1-3h to finally obtain the modified nano-cellulose.
The problem of poor dispersibility of the nanocrystalline cellulose in the acrylic resin can occur when the nanocrystalline cellulose is directly added into the acrylic resin to prepare the nanocrystalline cellulose modified acrylic resin. Therefore, the nanocrystalline cellulose is modified, specifically, an ester imidazole intermediate with reaction activity is formed by the reaction of an alcohol functional group between a surfactant and the nanocrystalline cellulose, so that hydroxyl of the nanocrystalline cellulose is substituted by allyl carbonate, and then the modified nanocrystalline cellulose containing the allyl carbonate is obtained. The modified nano-crystalline cellulose filler has good dispersibility in acrylic resin, so that the nano-crystalline cellulose filler and the acrylic resin have better composite effect, and the prepared nano-crystalline cellulose modified acrylic resin system has good mechanical property. When the nanocrystalline cellulose is modified, the heating temperature and the stirring speed in the step S2 need to be strictly controlled, so that the nanocrystalline cellulose is conveniently modified under the low-temperature condition, and the nanocrystalline cellulose is further favorably modified.
Preferably, each part of the bactericide is at least one of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride; more preferably, each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 0.8-1.2:0.6-1.0: 0.4-0.8. Each part of the coupling agent is any one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane and triglycidyl ether oxypropyltrimethoxysilane.
The bactericide of the invention is a mixed bactericide consisting of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 0.8-1.2:0.6-1.0:0.4-0.8, and can cooperate with the excellent antibacterial performance of the three, and obviously improve the antibacterial and corrosion-resistant performance of an acrylic resin system. The adopted method can enable the modified nano-cellulose and the acrylic resin to be combined more closely, and the stability of the finally modified acrylic resin system is obviously improved.
Preferably, each part of the antioxidant is at least two of antioxidant DNP, antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703. More preferably, each part of the antioxidant is a mixture of the antioxidant DNP, the antioxidant 1010 and the antioxidant 168 according to the weight ratio of 0.6-1.0:0.4-0.8: 0.8-1.2.
The antioxidant 1010 adopted by the invention has excellent antioxidant performance on acrylic resin, the antioxidant 1010 can effectively prevent the acrylic resin from thermal oxidation degradation in the long-term aging process, so that the service life of the nano-cellulose modified acrylic resin is prolonged, and in addition, the antioxidant 1010 and the antioxidant 168 can be used together to have a synergistic effect; the antioxidant 168 and the antioxidant DNP3 are auxiliary antioxidants of the antioxidant 1010, are compounded with the main antioxidant 1010, have good synergistic effect, can effectively prevent the thermal degradation of the acrylic resin in basic injection molding, and provide extra long-acting protection for the modified acrylic resin system.
Preferably, each part of the solvent is at least one of water, methanol, ethanol, isopropanol, N-butanol, N-methylpyrrolidone, dimethyl sulfoxide and pyridine. Each part of the filler is at least one of silicon lime, aluminum powder and zinc powder.
The solvent adopted in the invention has good dissolving effect, and can well mutually compatibilize all the raw materials in the process of modifying the acrylic resin, thereby improving the efficiency of modifying the acrylic resin.
The invention also provides a preparation method of the nano-cellulose modified acrylic resin, which comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 50-70 ℃ in a nitrogen atmosphere, and stirring for 20-40min to obtain a mixture A for later use;
2) according to the parts by weight, the methallyl alcohol, the coupling agent, the bactericide and the filler are mixed and stirred uniformly, and are heated to 80-100 ℃ and are continuously stirred for 30-60min under the condition of 500r/min and 400-;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 30-60min at 50-70 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The nano-cellulose modified acrylic resin prepared by the method has the characteristics of excellent strength, elasticity and wear resistance, high curing speed, better mechanical property and chemical corrosion resistance, strong adhesive force, good ductility, high temperature resistance and long service life. In the process of preparing the nano-cellulose modified acrylic resin, the temperature in the step 1) needs to be strictly controlled to be 50-70 ℃, if the temperature is too high, part of solvent is volatilized, if the temperature is too low, the diffusion activity among raw material molecules is reduced, the dispersion among the raw materials is not facilitated, and further the comprehensive performance of a nano-cellulose modified acrylic resin system is influenced; and the temperature in the step 3) needs to be strictly controlled to be 50-70 ℃, if the temperature is too high, the interface molecules of the modified nano-cellulose are too active, and the interface binding force between the modified nano-cellulose and the acrylic resin is not facilitated.
The invention also provides decorative paper which is prepared by adopting the nano-cellulose modified acrylic resin.
The decorative paper is prepared by adopting the nano-cellulose modified acrylic resin, so that the decorative paper has good antibacterial, antioxidant, weather-resistant and heat-resistant effects, and the decorative paper with excellent performance is obtained.
The invention has the beneficial effects that: the nanocellulose modified acrylic resin has obvious modified nanocellulose effect, can be well dispersed in an acrylic resin matrix to improve the effect of a two-phase interface, so that the prepared nanocellulose modified acrylic resin has excellent strength, elasticity and wear resistance, is high in curing speed, and has the characteristics of good mechanical property, good chemical corrosion resistance, strong adhesive force, good ductility, high temperature resistance and long service life.
The preparation method of the nano-cellulose modified acrylic resin has the advantages of simple operation, convenient control, high production efficiency and low production cost.
The decorative paper is prepared by adopting the nano-cellulose modified acrylic resin, so that the decorative paper has good antibacterial, antioxidant, weather-resistant and heat-resistant effects, and the decorative paper with excellent performance is obtained.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
Each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
The modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 40 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 40 ℃, and stirring at the speed of 250r/min for 1h to finally obtain the modified nanocellulose.
Each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 0.8:0.6: 0.4.
Each part of the coupling agent is aminopropyl triethoxysilane.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.6:0.4: 0.8.
Each of the solvents was methanol.
Each part of the filler is silicon lime.
The preparation method of the nano-cellulose modified acrylic resin comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 50 ℃ in a nitrogen atmosphere, and stirring for 20min to obtain a mixture A for later use;
2) mixing and stirring the methallyl alcohol, the coupling agent, the bactericide and the filler uniformly according to the parts by weight, heating to 80 ℃, and continuously stirring for 30min under the condition of 400r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 30min at 50 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The decorative paper is prepared from the nano-cellulose modified acrylic resin.
Example 2
The nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
Each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
The modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 45 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 45 ℃, and stirring at the speed of 260r/min for 1.5h to finally obtain the modified nanocellulose.
Each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 0.9:0.7: 0.5.
Each part of the coupling agent is aminopropyl trimethoxy silane.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.7:0.5: 0.9.
Each part of the solvent is ethanol.
Each part of the filler is aluminum powder.
The preparation method of the nano-cellulose modified acrylic resin comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 55 ℃ in a nitrogen atmosphere, and stirring for 25min to obtain a mixture A for later use;
2) mixing and stirring the methallyl alcohol, the coupling agent, the bactericide and the filler uniformly according to the parts by weight, heating to 85 ℃, and continuously stirring for 38min under the condition of 425r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 38min at the temperature of 55 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The decorative paper is prepared from the nano-cellulose modified acrylic resin.
Example 3
The nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
Each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
The modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 50 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 5 ℃, and stirring at the speed of 270r/min for 2 hours to finally obtain the modified nanocellulose.
Each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 1.0:0.8: 0.6.
Each part of the coupling agent is triglycidyl ether oxypropyl trimethoxy silane.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.8:0.6: 1.0.
Each part of the solvent is n-butanol.
Each part of the filler is zinc powder.
The preparation method of the nano-cellulose modified acrylic resin comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 60 ℃ in a nitrogen atmosphere, and stirring for 30min to obtain a mixture A for later use;
2) according to the parts by weight, the methallyl alcohol, the coupling agent, the bactericide and the filler are uniformly mixed and stirred, and are heated to 90 ℃ and continuously stirred for 45min under the condition of 450r/min, so as to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 45min at the temperature of 60 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The decorative paper is prepared from the nano-cellulose modified acrylic resin.
Example 4
The nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
Each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
The modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 55 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 55 ℃, and stirring at the speed of 280r/min for 2.5 hours to finally obtain the modified nanocellulose.
Each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 1.1:0.9: 0.7.
Each part of the coupling agent is aminopropyl triethoxysilane.
Each part of the antioxidant is a mixture of an antioxidant DNP, an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 0.9:0.7: 1.1.
Each part of the solvent is N-methyl pyrrolidone.
Each part of the filler is silicon lime.
The preparation method of the nano-cellulose modified acrylic resin comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 65 ℃ in a nitrogen atmosphere, and stirring for 35min to obtain a mixture A for later use;
2) mixing and stirring the methallyl alcohol, the coupling agent, the bactericide and the filler uniformly according to the parts by weight, heating to 95 ℃, and continuously stirring for 52min under the condition of 475r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 52min at 65 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The decorative paper is prepared from the nano-cellulose modified acrylic resin.
Example 5
The nano-cellulose modified acrylic resin comprises the following raw materials in parts by weight:
the acrylic resin is MB2660 acrylic resin produced by chemical engineering company Limited in Shanghai.
Each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
the surfactant is N, N-carbonyl diimidazole.
The modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 60 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 60 ℃, and stirring at the speed of 300r/min for 1-3h to finally obtain the modified nanocellulose.
Each part of the bactericide is a mixture of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride according to the weight ratio of 1.2:1.0: 0.8.
Each part of the coupling agent is aminopropyl trimethoxy silane.
Each part of the antioxidant is a mixture of antioxidant DNP, antioxidant 1010 and antioxidant 168 according to the weight ratio of 1.0:0.8: 1.2.
Each part of the solvent is dimethyl sulfoxide.
Each part of the filler is aluminum powder.
The preparation method of the nano-cellulose modified acrylic resin comprises the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 70 ℃ in a nitrogen atmosphere, and stirring for 40min to obtain a mixture A for later use;
2) mixing and stirring the methallyl alcohol, the coupling agent, the bactericide and the filler uniformly according to the parts by weight, heating to 100 ℃, and continuously stirring for 60min under the condition of 500r/min to obtain a mixture B for later use;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 60min at the temperature of 70 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
The decorative paper is prepared from the nano-cellulose modified acrylic resin.
Comparative example 1
This comparative example differs from example 1 above in that: no modification of the nanocrystalline cellulose was performed in this comparative example. The remainder of this comparative example is the same as example 1 and will not be described again here.
Comparative example 2
This comparative example differs from example 3 above in that: in this comparative example, no surfactant was added during the preparation of the modified nanocellulose, and the remaining raw materials were mixed in the proportions of example 3. The remainder of this comparative example is the same as example 3 and will not be described again here.
Comparative example 3
This comparative example differs from example 5 above in that: no biocide was added in this comparative example. The remainder of this comparative example is the same as example 5 and will not be described again here.
The nanocellulose modified acrylic resins obtained in examples 1 to 5 and comparative examples 1 to 3 were coated, the coating weight was controlled at 15g/m2, after drying, the nanocellulose modified acrylic resins were plasticized and embossed at 135 ℃, after cooling and forming, the abrasion resistance, the edge pressure strength (GB/T6544-:
antibacterial property test antibacterial property was tested according to JISZ2801: 2010.
And (3) moisture regain testing: the coating is placed for 24 hours at the high humidity of 40 ℃ and 95 percent of humidity, the moisture regain of the paper product is measured by using a DM200P nondestructive induction type paper moisture meter to respectively measure the water content of the coating on the nano cellulose modified acrylic resin prepared by implementing 1-5 and the nano cellulose modified acrylic resin prepared by implementing 1-3 in comparison examples, the instrument adopts the high frequency principle, the simple contact instantaneous reading can be realized, and the moisture regain of the paper can be obtained. And then the tensile strength meter and the tearing strength meter are used for detecting the paper indexes.
TABLE 1
| Item | Dry friction (grade) | Wet friction (grade) | Antibacterial ratio (%) | Edge pressure intensity (N/m) | Moisture regain (%) |
| Example 1 | 4 | 4 | 98.23 | 18112 | 2.3 |
| Example 2 | 4 | 4 | 98.38 | 18127 | 2.5 |
| Example 3 | 4 | 4 | 98.89 | 18135 | 2.4 |
| Example 4 | 4 | 4 | 98.54 | 18144 | 2.3 |
| Practice ofExample 5 | 4 | 4 | 98.63 | 18133 | 2.4 |
| Comparative example 1 | 3.4 | 3.6 | 84.3 | 14830 | 1.40 |
| Comparative example 2 | 3.7 | 3.6 | 90.3 | 16754 | 1.6 |
| Comparative example 3 | 4 | 4 | 86.4 | 18975 | 1.8 |
From the above, the nanocellulose modified acrylic resin of the invention has excellent wear resistance, edge pressure strength, antibacterial rate and moisture regain. According to the invention, the modified nanocellulose and the bactericide are added into the nanocellulose modified acrylic resin, and the surfactant is added when the nanocrystaline cellulose is modified, so that the prepared nanocellulose modified acrylic resin has excellent strength, elasticity and wear resistance, is high in curing speed, and has the characteristics of good mechanical property, good chemical corrosion resistance, strong adhesive force, good ductility, high temperature resistance and long service life.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A nano-cellulose modified acrylic resin is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the nanocellulose-modified acrylic resin of claim 1, wherein: each part of the modified nano-cellulose comprises the following raw materials in parts by weight:
3. the nanocellulose-modified acrylic resin of claim 2, wherein: the modified nano-cellulose is prepared by the following method:
s1, adding the nano microcrystalline cellulose into a mixture of N, N-dimethylformamide and 4-dimethylaminopyridine according to parts by weight, heating the mixture to 40-60 ℃, uniformly stirring the mixture, transferring the mixture into a ball mill, and grinding the mixture to obtain a mixture A for later use;
s2, transferring the mixture A obtained in the step S1 to a heating device, adding a surfactant, heating to 40-60 ℃, and stirring at the speed of 250-300r/min for 1-3h to finally obtain the modified nano-cellulose.
4. The nanocellulose-modified acrylic resin of claim 1, wherein: each part of the bactericide is at least one of phenyl bromoacetate, sodium dimethyldithiocarbamate and silver chloride.
5. The nanocellulose-modified acrylic resin of claim 1, wherein: each part of the coupling agent is any one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane and triglycidyl ether oxypropyltrimethoxysilane.
6. The nanocellulose-modified acrylic resin of claim 1, wherein: each part of the antioxidant is at least two of antioxidant DNP, antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703.
7. The nanocellulose-modified acrylic resin of claim 1, wherein: each part of the solvent is at least one of water, methanol, ethanol, isopropanol, N-butanol, N-methylpyrrolidone, dimethyl sulfoxide and pyridine.
8. The nanocellulose-modified acrylic resin of claim 1, wherein: each part of the filler is at least one of silicon lime, aluminum powder and zinc powder.
9. A method for preparing the nanocellulose-modified acrylic resin according to any one of claims 1 to 8, characterized in that: is prepared by the following steps:
1) adding the modified nano-cellulose, acrylic resin, hydroxy cellulose and a solvent into a stirrer according to parts by weight, heating to 50-70 ℃ in a nitrogen atmosphere, and stirring for 20-40min to obtain a mixture A for later use;
2) according to the parts by weight, the methallyl alcohol, the coupling agent, the bactericide and the filler are mixed and stirred uniformly, and are heated to 80-100 ℃ and are continuously stirred for 30-60min under the condition of 500r/min and 400-;
3) adding the mixture B obtained in the step 2) and an antioxidant into the mixture A obtained in the step 1), keeping the temperature and stirring for 30-60min at 50-70 ℃, discharging and cooling to obtain the nano-cellulose modified acrylic tree.
10. A decorative paper characterized by: the decorative paper is made from the nano cellulose modified acrylic resin as described in any one of claims 1-8.
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| CN113857427A (en) * | 2021-10-13 | 2021-12-31 | 东莞市化工学会 | Precision casting mold material and preparation method thereof |
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