Disclosure of Invention
The invention aims to solve the technical problem of providing a nano-cellulose detergent which is simple in formula, low in cost, environment-friendly and mild in washing condition, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a nano-cellulose detergent, which comprises the following components in parts by mass:
6-10 parts of polycarboxylic acid modified nano-cellulose
0-4 parts of carboxymethyl cellulose
60-100 parts of surfactant
0 to 1 part of saponin
20-40 parts of water.
Preferably, the polycarboxylic acid used for preparing the polycarboxylic acid modified nano-cellulose is one or more of maleic acid, citric acid and butane tetracarboxylic acid.
According to some specific and preferred embodiments, the polycarboxylic acid modified nanocellulose is prepared by mixing a cellulose raw material with water and polycarboxylic acid, and shearing and reacting. The reaction product is directly used as the polycarboxylic acid modified nano-cellulose, so that the raw material utilization rate is high, and the preparation is convenient.
Preferably, the feeding mass ratio of the cellulose raw material, the water and the polycarboxylic acid is 1: 15-100: 2 to 4, further 20 to 100, and further 20 to 50.
Preferably, the cellulosic raw material comprises one or more of bleached pulp, cotton pulp, microcrystalline cellulose. The cellulose of the invention is widely existed in nature, is a natural organic high molecular substance with good biocompatibility and can be recycled, the surface of the cellulose modified by polycarboxylic acid has oleophilic and hydrophilic groups, the emulsifying capacity is obviously improved, the capability of stabilizing Pickering emulsion is enhanced, and the decontamination capacity of the detergent can be obviously improved when the cellulose is applied to the detergent.
Preferably, the shearing speed is controlled to be 1000 to 30000rpm, further 5000 to 30000rpm, and further 5000 to 20000 rpm.
Further preferably, the shearing time is controlled to be 15-60 min, and further 20-30 min.
Preferably, the reaction temperature is controlled to be 100-140 ℃, and further 100-120 ℃.
Further preferably, the reaction time is controlled to be 10-20 h, and further 14-18 h.
Preferably, the surfactant comprises a betaine series surfactant.
Further preferably, the betaine series surfactant comprises one or more of dodecyl dimethyl betaine, cetyl betaine, cocamidopropyl betaine, lauramidopropyl betaine.
Preferably, the detergent further comprises a pH adjuster.
Preferably, the pH of the detergent is 3-5 or 8-10.
Further preferably, the pH adjusting agent is citric acid or sodium carbonate. The detergent can be prepared into weak-acid or weak-alkaline washing liquid by adding different pH regulators, and can be further diluted when used for washing metal products, so that the washing condition of the detergent is mild, the surface quality and performance of a washed part cannot be damaged, and the service life of the washed part can be prolonged.
In a second aspect, the present invention provides a method for preparing the above-mentioned nano cellulose detergent, wherein the nano cellulose detergent is prepared by mixing, shearing and homogenizing polycarboxylic acid modified nano cellulose, water, a surfactant, and/or carboxymethyl cellulose, and/or saponin, and/or a pH regulator.
Preferably, the shearing speed is controlled to be 1000-30000 rpm, further 10000-30000 rpm, and further 10000-20000 rpm.
Further preferably, the shearing time is controlled to be 15-30 min, and further 20-30 min.
Preferably, the homogenizing pressure is controlled to be 30-120 MPa.
Further preferably, the homogenization is a multiple homogenization.
According to some specific and preferred embodiments, the preparation method comprises the following steps:
(1) mixing, shearing and homogenizing the polycarboxylic acid modified nano-cellulose and the water to prepare polycarboxylic acid modified nano-cellulose dispersion liquid;
(2) selectively combining the carboxymethyl cellulose with the water to form an aqueous carboxymethyl cellulose solution;
(3) mixing, shearing and homogenizing the polycarboxylic acid nano-cellulose dispersion liquid in the step (1), the surfactant and/or the carboxymethyl cellulose aqueous solution in the step (2) and/or the saponin and/or the pH regulator.
Preferably, the mass concentration of the polycarboxylic acid modified nanocellulose dispersion in the step (1) is 10 to 50%, further 30 to 50%, and further 30 to 40%.
Preferably, the shearing speed in the step (1) is controlled to be 1000-30000 rpm, further 10000-30000 rpm, and further 10000-20000 rpm.
Further preferably, the shearing time in the step (1) is controlled to be 15-60 min, further 20-60 min, and further 20-30 min.
Preferably, the homogenizing pressure in the step (1) is controlled to be 30-120 MPa.
Further preferably, the homogenization in the step (1) is a plurality of times of homogenization.
Preferably, the shearing speed in the step (3) is 1000-30000 rpm, further 10000-30000 rpm, and further 10000-20000 rpm.
Further preferably, the shearing time in the step (3) is 15 to 30min, and further 20 to 30 min.
Preferably, the pressure for homogenizing in the step (3) is 30-120 MPa.
Further preferably, the homogenization in the step (3) is a plurality of times of homogenization.
In a third aspect of the invention, there is provided a use of the nano-cellulose detergent as described above and/or the nano-cellulose detergent prepared by the preparation method as described above in a metal product.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the nano-cellulose detergent disclosed by the invention is simple in formula and environment-friendly, and the polycarboxylic acid modified nano-cellulose in the detergent has oleophilic and hydrophilic groups, so that the detergent is good in emulsifying capacity and strong in dirt-removing power.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples.
The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other. The plural times in the present invention means two times or more unless otherwise specified.
According to the invention, the polycarboxylic acid modified nano-cellulose with both oleophilic and hydrophilic groups is adopted, so that a good washing effect can be obtained only by compounding the polycarboxylic acid modified nano-cellulose with a few auxiliary agents under the condition of only adding a small amount of the polycarboxylic acid modified nano-cellulose, and the detergent has the advantages of simple overall formula components and low cost.
Example one
The nano-cellulose detergent comprises the following components in parts by mass:
10 parts of citric acid modified nano-cellulose, 2 parts of carboxymethyl cellulose, 100 parts of dodecyl dimethyl betaine, 1 part of saponin and 37 parts of deionized water, wherein the total mass part is 150 parts.
In this embodiment, the specific preparation process of the citric acid modified nanocellulose is as follows: weighing 1 time of bleached pulp fiber, adding deionized water to prepare a dispersion liquid with the mass concentration of 2%, adding 4 times of anhydrous citric acid, shearing at a high speed of 20000rpm for 30min, pouring into a stainless steel open container, placing in a forced air drying oven, and reacting at 120 ℃ for 16h to obtain the citric acid modified nanocellulose.
In this example, the detergent was prepared as follows:
(1) weighing 10 parts of citric acid modified nano-cellulose, adding 19 parts of deionized water, shearing at a high speed of 20000rpm for 30min, carrying out primary granularity refinement, then carrying out high-pressure homogenization, sequentially homogenizing for 1 time at 30MPa, 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120MPa to obtain 29 parts of citric acid modified nano-cellulose dispersion liquid;
(2) weighing 2 parts of carboxymethyl cellulose and 18 parts of deionized water, adding the carboxymethyl cellulose into the deionized water under a stirring state until the carboxymethyl cellulose is completely dissolved to obtain 20 parts of carboxymethyl cellulose aqueous solution;
(3) adding 29 parts of citric acid modified nano cellulose dispersion liquid, 20 parts of carboxymethyl cellulose aqueous solution, 100 parts of dodecyl dimethyl betaine and 1 part of saponin into a reaction container in sequence, stirring and mixing uniformly, shearing at a high speed of 20000rpm for 30min, then homogenizing at high pressure, homogenizing at 30MPa for 1 time, 60MPa for 1 time, 80MPa for 2 times, 100MPa for 2 times and 120MPa for 2 times in sequence to obtain 150 parts of detergent, wherein the appearance diagram of the detergent is shown in figure 2.
In this example, the detergent was used as follows: weighing 1kg of detergent, adding warm water at 40 ℃ for diluting by 70 times to 70kg, namely diluting to the concentration of 1.4%, immersing the metal piece to be washed in the detergent, and carrying out ultrasonic treatment at 200Hz for 2min to clean the metal piece, wherein the outer surface of the washed metal piece is bright as new, and the original metal luster is kept. The metal piece to be cleaned in this embodiment is shown in fig. 3, and the metal piece after washing is shown in fig. 4.
The embodiment is suitable for cleaning an oil stain aluminum shell, and the used metal piece is provided by a certain capacitor company in Nantong.
Example two
The nano-cellulose detergent comprises the following components in parts by mass:
8 parts of citric acid modified nano-cellulose, 4 parts of carboxymethyl cellulose, 80 parts of dodecyl dimethyl betaine, 1 part of saponin, 4 parts of citric acid and 38 parts of deionized water, wherein the total mass part is 135 parts.
In this embodiment, the specific preparation process of the citric acid modified nanocellulose is as follows: weighing 1 time of cotton pulp fiber, adding deionized water to prepare a dispersion liquid with the mass concentration of 3%, adding 3 times of anhydrous citric acid, shearing at a high speed of 20000rpm for 20min, pouring into a stainless steel open container, placing in a forced air drying oven, and reacting at 120 ℃ for 14h to obtain the citric acid modified nanocellulose.
In this example, the detergent was prepared as follows:
(1) weighing 8 parts of citric acid modified nano-cellulose, adding 12 parts of deionized water, shearing at a high speed of 10000rpm for 20min, carrying out primary granularity refinement, then carrying out high-pressure homogenization, sequentially homogenizing for 1 time at 30MPa, 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120MPa to obtain 20 parts of citric acid modified nano-cellulose dispersion liquid;
(2) weighing 4 parts of carboxymethyl cellulose and 26 parts of deionized water, adding the carboxymethyl cellulose into the deionized water under a stirring state until the carboxymethyl cellulose is completely dissolved to obtain 30 parts of carboxymethyl cellulose aqueous solution;
(3) sequentially adding 20 parts of citric acid modified nano cellulose dispersion liquid, 30 parts of carboxymethyl cellulose aqueous solution, 80 parts of dodecyl dimethyl betaine and 1 part of saponin into a reaction container, stirring and mixing uniformly, shearing at 10000rpm for 20min at a high speed, then homogenizing at high pressure, sequentially homogenizing at 60MPa for 1 time, 80MPa for 2 times, 100MPa for 2 times and 120MPa for 2 times;
(4) 4 parts of citric acid was added to adjust the pH to 4, to obtain 135 parts of a detergent.
In this example, the detergent was used as follows: weighing 1kg of detergent, adding warm water at 40 ℃ for diluting by 100 times to 100kg, namely diluting to the concentration of 1.0%, immersing the metal piece to be washed in the detergent, and carrying out ultrasonic treatment at 200Hz for 2min to clean the metal piece, wherein the inner surface and the outer surface of the washed metal piece are bright as new, and the original color and brightness are maintained.
The embodiment is suitable for cleaning greasy dirt aluminum shells and stearic acid zinc dust dirt aluminum shells, and the used metal piece is provided by a certain capacitor company in Nantong.
EXAMPLE III
The nano-cellulose detergent comprises the following components in parts by mass:
6 parts of citric acid modified nano-cellulose, 4 parts of carboxymethyl cellulose, 60 parts of cocamidopropyl betaine, 1 part of saponin, 4 parts of sodium carbonate and 40 parts of deionized water, wherein the total mass part is 115 parts.
In this embodiment, the specific preparation process of the citric acid modified nanocellulose is as follows: weighing 1 time of microcrystalline cellulose, adding deionized water to prepare a dispersion liquid with the mass concentration of 5%, adding 2 times of anhydrous citric acid, shearing at a high speed of 5000rpm for 60min, pouring into a stainless steel open container, placing in a forced air drying oven, and reacting at 100 ℃ for 18h to obtain the citric acid modified nanocellulose.
In this example, the detergent was prepared as follows:
(1) weighing 6 parts of citric acid modified nano-cellulose, adding 14 parts of deionized water, shearing at a high speed of 10000rpm for 20min, carrying out primary granularity refinement, then carrying out high-pressure homogenization, sequentially homogenizing for 1 time at 30MPa, 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120MPa to obtain 20 parts of citric acid modified nano-cellulose dispersion liquid;
(2) weighing 4 parts of carboxymethyl cellulose and 26 parts of deionized water, adding the carboxymethyl cellulose into the deionized water under a stirring state until the carboxymethyl cellulose is completely dissolved to obtain 30 parts of carboxymethyl cellulose aqueous solution;
(3) sequentially adding 20 parts of citric acid modified nano cellulose dispersion liquid, 30 parts of carboxymethyl cellulose aqueous solution, 60 parts of cocamidopropyl betaine and 1 part of saponin into a reaction container, stirring and mixing uniformly, shearing at a high speed of 10000rpm for 20min, then homogenizing at high pressure, sequentially homogenizing at 60MPa for 1 time, 80MPa for 2 times, 100MPa for 2 times and 120MPa for 2 times;
(4) 4 parts of sodium carbonate was added to adjust the pH to 9, to obtain 115 parts of a detergent.
In this example, the detergent was used as follows: weighing 1kg of detergent, adding 50-DEG C warm water to dilute the detergent by 50 times to 50kg, namely diluting the detergent to the concentration of 2.0%, immersing the metal piece to be washed in the detergent, and carrying out ultrasonic treatment at 200Hz for 2min to clean the metal piece, wherein the inner surface and the outer surface of the washed metal piece are bright as new, and the original metal luster is kept.
The embodiment is suitable for cleaning heavy oil polluted aluminum shells, and the metal piece is provided by a certain capacitor company in Nantong.
Example four
The nano-cellulose detergent comprises the following components in parts by mass:
10 parts of maleic acid modified nano-cellulose, 100 parts of lauramidopropyl betaine, 1 part of saponin, 4 parts of sodium carbonate and 20 parts of deionized water, wherein the total mass part is 135 parts.
In this embodiment, the specific preparation process of the maleic acid modified nanocellulose is as follows: weighing 1 time of microcrystalline cellulose, adding deionized water to prepare a dispersion liquid with the mass concentration of 5%, adding 2 times of maleic acid, shearing at a high speed of 5000rpm for 60min, pouring into a stainless steel open container, placing in a forced air drying oven, and reacting at 100 ℃ for 18h to obtain the maleic acid modified nanocellulose.
In this example, the detergent was prepared as follows:
(1) weighing 10 parts of maleic acid modified nano-cellulose, adding 20 parts of deionized water, shearing at a high speed of 10000rpm for 20min, carrying out primary granularity refinement, then carrying out high-pressure homogenization, sequentially homogenizing for 1 time at 30MPa, 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120MPa to obtain 30 parts of maleic acid modified nano-cellulose dispersion liquid;
(2) sequentially adding 30 parts of maleic acid modified nano cellulose dispersion liquid, 100 parts of lauramidopropyl betaine and 1 part of saponin into a reaction container, stirring and mixing uniformly, shearing at a high speed of 10000rpm for 20min, then homogenizing at high pressure sequentially for 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120 MPa;
(3) 4 parts of sodium carbonate was added to adjust the pH to 10, to obtain 135 parts of a detergent.
In this example, the detergent was used as follows: weighing 1kg of detergent, adding 50-DEG C warm water to dilute the detergent by 50 times to 50kg, namely diluting the detergent to the concentration of 2.0%, immersing the metal piece to be washed in the detergent, and carrying out ultrasonic treatment at 200Hz for 2min to clean the metal piece, wherein the inner surface and the outer surface of the washed metal piece are bright as new, and the original metal luster is kept.
The embodiment is suitable for cleaning heavy oil polluted aluminum shells, and the metal piece is provided by a certain capacitor company in Nantong.
EXAMPLE five
The nano-cellulose detergent comprises the following components in parts by mass:
10 parts of butane tetracarboxylic acid modified nano-cellulose, 4 parts of carboxymethyl cellulose, 40 parts of each of cocamidopropyl betaine and hexadecyl betaine, 4 parts of citric acid and 42 parts of deionized water, wherein the total mass part is 140 parts.
In this example, the specific preparation process of the butane tetracarboxylic acid modified nanocellulose is as follows: weighing 1 time of microcrystalline cellulose, adding deionized water to prepare a dispersion liquid with the mass concentration of 3%, adding 3 times of butanetetracarboxylic acid, shearing at a high speed of 20000rpm for 20min, pouring into a stainless steel open container, placing in a forced air drying oven, and reacting at 120 ℃ for 14h to obtain the butanetetracarboxylic acid modified nanocellulose.
In this example, the detergent was prepared as follows:
(1) weighing 10 parts of butane tetracarboxylic acid modified nano-cellulose, adding 16 parts of deionized water, shearing at a high speed of 10000rpm for 20min, carrying out primary granularity refinement, then carrying out high-pressure homogenization, sequentially homogenizing for 1 time at 30MPa, 1 time at 60MPa, 2 times at 80MPa, 2 times at 100MPa and 2 times at 120MPa to obtain 26 parts of butane tetracarboxylic acid modified nano-cellulose dispersion liquid;
(2) weighing 4 parts of carboxymethyl cellulose and 26 parts of deionized water, adding the carboxymethyl cellulose into the deionized water under a stirring state until the carboxymethyl cellulose is completely dissolved to obtain 30 parts of carboxymethyl cellulose aqueous solution;
(3) sequentially adding 26 parts of butane tetracarboxylic acid modified nano cellulose dispersion liquid, 30 parts of carboxymethyl cellulose aqueous solution, 40 parts of hexadecyl betaine and 40 parts of cocamidopropyl betaine into a reaction vessel, uniformly stirring and mixing, shearing at a high speed of 10000rpm for 20min, then homogenizing at high pressure, sequentially homogenizing at 60MPa for 1 time, homogenizing at 80MPa for 2 times, homogenizing at 100MPa for 2 times and homogenizing at 120MPa for 2 times;
(4) 4 parts of citric acid was added thereto, and the pH was adjusted to 3 to obtain 140 parts of a detergent.
In this example, the detergent was used as follows: weighing 1kg of detergent, adding warm water at 40 ℃ for diluting by 100 times to 100kg, namely diluting to the concentration of 1.0%, immersing the metal piece to be washed in the detergent, and carrying out ultrasonic treatment at 200Hz for 2min to clean the metal piece, wherein the inner surface and the outer surface of the washed metal piece are bright as new, and the original color and brightness are maintained.
The embodiment is suitable for cleaning greasy dirt aluminum shells and stearic acid zinc dust dirt aluminum shells, and the used metal piece is provided by a certain capacitor company in Nantong.
Comparative example 1
In the first embodiment, unmodified nano-cellulose is used for replacing citric acid modified nano-cellulose to prepare a detergent, other components and the proportion are unchanged, the preparation process is unchanged, the detergent is found to be easy to delaminate after standing for a long time in the preparation process, the detergent is used for a washing experiment after shaking up, the detergent is diluted to the concentration of 1.4%, a metal piece to be washed is immersed in the detergent, ultrasonic treatment is carried out for 2min at 200Hz, and local stubborn stains are not cleaned up after washing, and the first embodiment is shown in a first comparative example of figure 5. Indicating a decrease in its washing ability.
Comparative example No. two
In the first embodiment, TEMPO oxidized nano-cellulose is used for replacing citric acid modified nano-cellulose to prepare a detergent, other components and the proportion are unchanged, the preparation process is unchanged, the detergent is found to be easy to delaminate after standing for a long time in the preparation process, the detergent is used for carrying out a washing experiment after shaking uniformly, the detergent is diluted to the concentration of 1.4%, a metal piece to be washed is immersed in the detergent, ultrasonic treatment is carried out for 2min at 200Hz, and local stubborn stains are not cleaned after washing, and the second embodiment is shown in figure 5-a comparative example. Indicating a decrease in its washing ability.
Comparative example No. three
In the first example, the detergent was prepared without adding citric acid modified nanocellulose, the other components and the ratio were unchanged, the preparation process was unchanged, it was found in the preparation process that the metal piece to be washed was diluted to a concentration of 1.4%, immersed therein, subjected to 200Hz ultrasound for 2min, and many stubborn stains were not cleaned after washing, see fig. 5-comparative example three. The washing capacity of the prepared detergent is greatly reduced, which shows that the modified nano-cellulose has obvious effect on improving the washing efficiency.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.