CN109836892B - Easy-to-wipe nano dust-free chalk and preparation method thereof - Google Patents
Easy-to-wipe nano dust-free chalk and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of cultural and educational supplies and stationery supplies, in particular to an easily-erasable nano dust-free chalk and a preparation method thereof. An easy-to-wipe nano dust-free chalk at least comprises the following components in parts by weight: 50-80 parts of titanium dioxide; 1-15 parts of white oil; 1-12 parts of silicone oil; 1-12 parts of paraffin; 10-40 parts of an auxiliary agent; wherein the auxiliary agent consists of alkane modified chitosan and monoglyceride. The dustless chalk has the advantages that through the mutual synergistic effect of the components such as titanium dioxide, white oil, paraffin, an auxiliary agent and the like, the quality is fine and flexible, the writing is smooth, and the breakage is not easy to occur; the total dust concentration of the chalk is greatly reduced by controlling the proportion of each component. Moreover, the dust-free chalk does not contain toxic and volatile substances, has good weather resistance and long service life, has proper adhesive force of writing and is easy to erase, thereby being beneficial to the improvement of the teaching environment.
Description
Technical Field
The invention relates to the field of cultural and educational supplies and stationery supplies, in particular to an easily-erasable nano dust-free chalk and a preparation method thereof.
Background
The chalk is an indispensable cultural article in daily teaching, and is widely used due to the advantages of clear and intuitive fonts, easy writing and erasing, low price and the like. Gypsum powder is the most widely used raw material for making chalk, and is the white base material of chalk and the binder for forming chalk. But the gypsum chalk has pores and small density (0.8-1.0 g/cm)3) The chalk is used for preparing common chalk, dust flies greatly in the using process, the body health of teachers and students is seriously harmed, and the environmental sanitation is influenced.
In order to improve the teaching environment and the use performance of chalks, dust-free chalks are widely used at home and abroad at present to solve the problem of dust pollution. At present, dust fall ways of home and abroad chalks mainly have two aspects: (1) increasing the weight of the powder; by adding grease or polyalcohol as binder and adding large specific gravity filler, the specific gravity and volume of the dust are increased, and the dust is not easy to disperse. (2) The abrasion resistance of the chalk is increased (the friction is reduced). For example, patent No. 201510919174.2 discloses a green and environment-friendly dust-free chalk prepared by adding a dust-proof agent, a higher fatty alcohol sulfate surfactant, medical stone powder, a processing aid and the like into gypsum powder; according to the patent with the application number of 201310386442.X, the environment-friendly dust-free chalk which is fluent in writing, clear in writing, moderate in hardness and less in dust is prepared by adding white powder, polyvinyl acetate emulsion, polyvinyl alcohol and the like into plaster. According to the patent with the application number of 200910011700.X, illite powder, glycerin, a surfactant, essential oil, edible oil, paraffin, plant palm oil and the like are added to prepare the biochemical chalk which does not generate dust and can be wiped clean by using a wet cloth. In fact, dust-free chalk still generates more or less dust because chalk writing is written by covering dust, but the dust amount is greatly reduced compared with that of ordinary chalk. In addition, the mechanical strength of the chalk is reduced due to the addition of the binding agents such as grease and the like, and the writing of the chalk is firmly adhered to the blackboard and is not easy to erase, so that the use is inconvenient and the popularization is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides an easy-to-erase nano dust-free chalk, which at least comprises the following components in parts by weight:
wherein the auxiliary agent consists of alkane modified chitosan and monoglyceride.
As a preferred technical scheme, the titanium dioxide is rutile type titanium dioxide and/or anatase type titanium dioxide.
As a preferable technical scheme, the paraffin is paraffin modified by benzene rings.
As a preferable technical scheme, the alkane modified chitosan is straight-chain alkane modified chitosan with 8-12 carbon atoms.
In a preferable embodiment, the alkane-modified chitosan is a linear alkane-modified chitosan having 10 to 12 carbon atoms.
As a preferable technical scheme, the auxiliary agent consists of 20-50 wt% of alkane modified chitosan and 50-80 wt% of monoglyceride.
As a preferable technical scheme, the auxiliary agent consists of 20-30 wt% of alkane modified chitosan and 70-80 wt% of monoglyceride.
As a preferable technical scheme, the monoglyceride is at least one of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
As a preferred technical scheme, the monoglyceride is glyceryl palmitate.
The second aspect of the invention provides a preparation method of the dust-free chalk, which at least comprises the following steps:
s1, adding white oil and paraffin into a stirring container in sequence, stirring for 1-2 hours at a rotating speed of 1500-2500 rpm and a temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, silicone oil and an auxiliary agent into the stirring container in the step S1, stirring at the rotating speed of 1500-2500 rpm and the temperature of 80-100 ℃ for 1.5-2 hours;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
Has the advantages that: the dustless chalk has the advantages that through the mutual synergistic effect of the components such as titanium dioxide, white oil, paraffin, an auxiliary agent and the like, the quality is fine and flexible, the writing is smooth, and the breakage is not easy to occur; the total dust concentration of the chalk is greatly reduced by controlling the proportion of each component. Moreover, the dust-free chalk does not contain toxic and volatile substances, has good weather resistance and long service life, has proper adhesive force of writing and is easy to erase, thereby being beneficial to the improvement of the teaching environment.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the problems, the invention provides an easy-to-wipe nano dust-free chalk which at least comprises the following components in parts by weight:
as a preferred embodiment, the dust-free chalk at least comprises the following components in parts by weight:
titanium white powder
Titanium dioxide is a polycrystalline inorganic compound, and the main component of the titanium dioxide is TiO2。TiO2Is a polycrystalline compound with dots arranged regularly. It is a kind of acidic amphoteric oxide with very stable chemical property. Hardly reacts with other elements and compounds at normal temperature, does not act on oxygen, ammonia, nitrogen, hydrogen sulfide, carbon dioxide and sulfur dioxide, is insoluble in water, fat, dilute acid, inorganic acid and alkali and only dissolves in hydrofluoric acid. Under the action of light, the titanium dioxide can generate continuous oxidation-reduction reaction and has photochemical activity.
The titanium dioxide in the application can be prepared by a sulfuric acid method. The sulfuric acid method is characterized in that sulfuric acid is used as a main raw material for producing titanium dioxide, firstly, a titanium sulfate solution is obtained, and most of impurity iron elements in the solution are removed through reduction and vacuum crystallization; heating the titanium liquid to a temperature close to boiling temperature to hydrolyze the titanium sulfate solution to obtain metatitanic acid precipitate; filtering the metatitanic acid precipitate to remove most of waste acid and harmful metal impurities; then, removing most of impurity metal elements in the metatitanic acid by one-to-two water washing; adding proper salt treating agent into metatitanic acid, filtering to remove most of water, and calcining metatitanic acid filter cake in a brick kiln to obtain primary titanium dioxide product. And carrying out post-treatment on the primary product to obtain a titanium dioxide product.
The titanium dioxide in the application can also be prepared by a chlorination method. The chlorination process is a process using chlorine gas as a main raw material. Firstly, hydrochloric acid or smelting is used for removing iron element in ilmenite to obtain a titanium raw material with high titanium content; then reacting the coke and chlorine with a titanium raw material to generate titanium tetrachloride; heating and purifying, and reacting with oxygen at high temperature to obtain rutile type titanium dioxide primary product. The rutile type titanium dioxide product is obtained by post-treatment of the primary products.
The titanium dioxide has three crystal forms, namely rutile type titanium dioxide, anatase type titanium dioxide and plate type titanium dioxide. Wherein, the plate-shaped titanium white powder is a very unstable crystal form, belongs to an orthorhombic system, and the crystal lattice consists of 8 units of TiO2And (4) forming. When the temperature rises to about 650 ℃, the plate-type titanium dioxide is converted into rutile-type titanium dioxide. At the temperature of 200-600 ℃, adopting alkyl titanium or sodium titanate and potassium hydroxide or sodium hydroxide asThe plate-type titanium dioxide can be prepared from the raw materials. The anatase titanium dioxide is a tetragonal crystal system, and the crystal lattice is formed by 4 units of TiO2The composition, diffraction angle is 25.5 degrees, and the shape is approximately regular octahedron. The rutile type titanium dioxide is a tetragonal crystal system, and the crystal lattice is formed by 2 units of TiO2Composition, diffraction angle was 27.5 degrees, and its crystals were fine and long and in the shape of a rhombus.
As a preferred embodiment, the titanium dioxide is rutile type titanium dioxide and/or anatase type titanium dioxide.
Preferably, the titanium dioxide is rutile type titanium dioxide.
White oil
White oil, also known as paraffin oil and mineral oil, is colorless, odorless, chemically inert and has good light stability. The white oil has a saturated hydrocarbon structure, is obtained by subjecting a high-boiling fraction (i.e., a lubricating oil fraction) obtained by petroleum fractionation to dewaxing, carbonization, neutralization, and activated clay refining, and is a mixture of liquid hydrocarbons, mainly a mixture of n-isoparaffins having C16 to C31, and contains approximately zero aromatic hydrocarbons, nitrogen, oxygen, sulfur, and the like. The white oil has good oxidation stability, chemical stability and light stability.
In a preferred embodiment, the kinematic viscosity of the white oil is 10 to 50mm2/s。
Preferably, the kinematic viscosity of the white oil is 12-16 mm2/s。
In the application, the kinematic viscosity of the white oil is determined by referring to the method of GB/T265-1988. The measuring step is that at the temperature of 40 ℃, a certain volume of white oil flows through the time of a calibrated glass capillary viscometer under the gravity, and the product of the capillary constant and the flow time of the viscometer is the kinematic viscosity of the white oil at the temperature of 40 ℃.
In this application, the white oil (model # 15) was purchased from Nissu oil Co., Ltd, Wuxi.
Silicone oil
Silicone oil generally refers to a linear polysiloxane product that remains in a liquid state at room temperature. Generally, the silicone oil is classified into methyl silicone oil and modified silicone oil. The most commonly used silicone oil is methyl silicone oil, all organic groups of the methyl silicone oil are methyl, and the methyl silicone oil has good chemical stability, insulating property and hydrophobic property. It is prepared through hydrolysis of dimethyldichlorosilane in water to obtain initial condensed ring body, cracking and rectifying to obtain low ring body, mixing the ring body, sealing agent and catalyst together to obtain various mixture with different polymerization degree, and vacuum distillation to eliminate low-boiling point matter to obtain silicone oil. The silicone oil has excellent heat resistance, electric insulation, weather resistance, hydrophobicity, physiological inertia and smaller surface tension, and in addition, has low viscosity-temperature coefficient, higher compression resistance, and some varieties also have radiation resistance. The silicone oil has many special properties, such as oxidation resistance, high flash point, small volatility, no corrosion to metal, no toxicity and the like.
According to the chemical structure, methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxy phenyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil, cyanogen-containing silicone oil and the like are classified; according to the application, damping silicone oil, diffusion pump silicone oil, hydraulic oil, insulating oil, heat transfer oil, brake oil and the like are available. It is often used as high-grade lubricating oil, shock-proof oil, insulating oil, defoaming agent, demoulding agent, polishing agent and vacuum diffusion pump oil, etc. Among various silicone oils, methyl silicone oil is most widely used, and is the most important variety of silicone oils, and methyl phenyl silicone oil is the second choice. Further, ethyl silicone oil, methylphenyl silicone oil, nitrile-containing silicone oil and the like are also available. The modified silicone oil can have special properties through modification of the silicone oil.
In a preferred embodiment, the silicone oil is a hydroxyl silicone oil.
In a preferred embodiment, the hydroxyl silicone oil contains 1 to 10 wt% of hydroxyl groups.
Preferably, the content of hydroxyl groups in the hydroxyl silicone oil is 2 wt%.
In the application, the method for measuring the hydroxyl content in the hydroxyl silicone oil comprises the following steps: weighing 1g of hydroxyl silicone oil into a 250mL iodine flask, adding 10.0mL of toluene to dissolve, transferring 25.0mL of 0.5 mol/L2, 4-toluene diisocyanate toluene solution and 1mL of 1% catalyst N, N-dimethyl cyclohexylamine toluene solution into the iodine flask by a pipette, covering the iodine flask tightly, shaking up the mixture, and standing the mixture for 10 min. Then adding 25.0mL of 1.00mol/L diethylamine toluene solution, covering and shaking up, standing for 10min, adding 20mL of isopropanol and 1-2 drops of bromocresol green indicator solution, and titrating with 0.50mol/L hydrochloric acid standard solution until the blue mutation is yellow. And simultaneously performing a blank test. The hydroxyl group content was calculated as follows:
m(-OH)＝[c×(V1-V0)×17.01×100]/[m×1000]；
wherein m is the mass (g) of the hydroxyl silicone oil;
c is the concentration (mol/L) of the hydrochloric acid standard solution;
V1the volume of hydrochloric acid standard solution (mL) consumed for the sample;
V0the volume of hydrochloric acid standard solution (mL) was consumed for the blank sample.
The hydroxyl silicone oil is purchased from Qingdao Xingsheng organic silicon new material Co.
As a preferred embodiment, the adjuvant consists of an alkane-modified chitosan and a monoglyceride.
Alkane modified chitosan
Chitosan (chitin), also known as chitin and chitosan, is a polysaccharide containing (1 → 4) β -N-acetyl-D-glucose building blocks, which is usually obtained by deacetylation of chitin widely present in crustaceans such as shrimp shells and crab shells, as well as algae, fungi and some mollusks, and is called chitosan when the deacetylation degree of chitin reaches 60% and is a deacetylated product soluble in dilute acid.
The chitosan in the application is white or light yellow powdery solid, and a molecular chain contains a large amount of active groups such as amino (-NH)2) Hydroxyl (-OH) group, which is chemically active, can be used as an efficient adsorbent for adsorbing heavy metal ions in solution, such as Cu2+、Cd2+、Co2+、Ni2+、Zn2+And the like, are highly desirable metal ion adsorbing materials.The chitosan has various excellent characteristics of degradability, biocompatibility, adsorbability, hygroscopicity, film-forming property, no toxicity and the like.
As used herein, the term "alkane-modified chitosan" refers to the-NH group in chitosan2Reacting with fatty aldehyde to generate Schiff base (-N ═ C-), and forming-N-C-, namely alkane modified chitosan under the action of a strong reducing agent.
The preparation method of the alkane modified chitosan comprises the following steps:
1) adding 15mmol of chitosan into a mixed solution of 100mL of 0.2mol/L acetic acid aqueous solution and 80mL of absolute ethyl alcohol, and swelling the solution to form a transparent viscous liquid, wherein the pH value is 5-6;
2) adding 15mmol of aliphatic aldehyde-ethanol solution and excessive reducing agent sodium cyanoborohydride at 800rpm, and continuously stirring for reaction for 24 hours;
3) and after the reaction is finished, adjusting the pH value to be 7-8 by using NaOH, separating out solid particles, performing suction filtration, washing by using a mixed solvent of ethanol and water, and drying to obtain the alkane modified chitosan.
Wherein the fatty aldehyde is at least one selected from octyl aldehyde, nonyl aldehyde, decyl aldehyde, n-undecyl aldehyde and n-dodecyl aldehyde.
In a preferred embodiment, the alkane-modified chitosan is a linear alkane-modified chitosan having 8 to 12 carbon atoms.
Preferably, the alkane modified chitosan is linear alkane modified chitosan with 10-12 carbon atoms.
In the application, the titanium dioxide has the advantages of high refractive index, good weather resistance, high whiteness and the like, but the titanium dioxide is difficult to disperse in an oily system due to more hydroxyl groups on the surface of the titanium dioxide. The applicant finds that the dispersibility of titanium dioxide in an oily system can be improved by adding the alkane modified chitosan, so that the content of the titanium dioxide is increased. The alkane modified chitosan has polar and nonpolar groups, on one hand, the polar group is connected with TiO2Forming strong interaction force; on the other hand, the nonpolar group interacts with the oily system, and the dispersion of the titanium dioxide in the oily system is promoted. In particular to chitosan modified by linear chain alkane with 8-12 atomic numbersThe dispersion of the titanium dioxide in an oily system is greatly improved.
Monoglyceride
In the present application, the term "monoglyceride" is a monoglyceride of fatty acids.
In the application, the fatty acid monoglyceride contains a lipophilic long-chain alkyl group and two hydrophilic hydroxyl groups, and has good surface activity.
In a preferred embodiment, the monoglyceride is at least one of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
In a preferred embodiment, the monoglyceride is a palmitic acid glyceride.
The applicant finds that the dispersibility of titanium dioxide in an oily system can be improved by adding the alkane modified chitosan, but the titanium dioxide contains a larger cyclic structure, so that the emulsifying speed is low, and the emulsifying effect is not ideal. And the arrangement speed of molecular chains is slow due to the large cyclic structure in the alkane modified chitosan, so that formed micelles are loose, and have larger particle size and poorer stability. The applicant finds that after the fatty acid monoglyceride is added, the emulsifying speed of the alkane modified chitosan can be accelerated, and the stability of the emulsifier is improved. The applicant believes that the possible reasons are that the fatty glyceride has a longer molecular chain structure, the chain segment is easy to rotate and change the conformation, the migration speed of the hydrophilic group and the hydrophobic group in the inorganic matter and the oil phase system respectively is higher, so that a looser interfacial film is formed at a higher speed, and the cavity generated by the movement of the fatty glyceride can supply the movement of the ring structure in the alkane modified chitosan and the speed of the adsorption on the inorganic matter, so that the emulsification speed is increased.
As a preferred embodiment, the auxiliary agent consists of 20-50 wt% of alkane modified chitosan and 50-80 wt% of monoglyceride.
As a preferred embodiment, the auxiliary agent consists of 20-30 wt% of alkane modified chitosan and 70-80 wt% of monoglyceride.
Under the irradiation of ultraviolet rays, electrons on the surface of the titanium dioxide powder can generate transition, so that oxygen atoms on crystal lattices lose two electrons to form nascent oxygen with strong oxidation effect, organic substances in contact with titanium dioxide can be oxidized, the performance of surrounding organic media is changed, the toughness of the chalk is poor, the chalk is easy to break, and the use performance of the chalk is influenced. The applicant has unexpectedly found that the addition of the alkane modified chitosan and the fatty acid monoglyceride can improve the weatherability of the chalk to a certain extent. The possible reasons are: the alkane modified chitosan and the fatty acid monoglyceride form a coating effect around the titanium dioxide, and electrons on the surface of the titanium dioxide are prevented from generating transition to generate nascent oxygen.
Paraffin wax
The paraffin is also called crystal wax, hydrocarbon mixture with 18-30 carbon atoms, and has straight chain paraffin (about 80-95%), and small amount of paraffin with individual branch chain and monocyclic naphthene with long side chain (the total content of both is below 20%). The paraffin is a flaky or needle crystal prepared by refining a lubricating oil fraction obtained by distilling crude oil with a solvent, dewaxing the lubricating oil fraction with the solvent or freezing and crystallizing the paraffin, squeezing and dewaxing the lubricating oil fraction to obtain a cerate, deoiling the cerate, and supplementing and refining the wax.
In a preferred embodiment, the paraffin wax is a benzene ring-modified paraffin wax.
The preparation method of the paraffin modified by the benzene ring at least comprises the following steps:
(1) adding 1g of paraffin and 0.2g of acrylic acid into a 250mL four-neck flask, heating, melting and stirring, adding 0.02g of initiator benzoyl peroxide, and then heating to 80 ℃ for reaction for 2 hours to obtain the acrylic acid modified paraffin.
(2) And (2) adding the acrylic acid modified paraffin wax obtained in the step (1) into 0.05-0.5 g of aniline and 1mg of zinc powder, heating to 80 ℃, reacting for 2-10 h, and performing suction filtration to obtain benzene ring modified paraffin wax.
In a preferred embodiment, the mass fraction of benzene rings in the benzene ring-modified paraffin wax is 5 to 30%.
Preferably, the mass fraction of benzene rings in the benzene ring-modified paraffin is 20%.
The detection method of the mass fraction of the benzene ring in the benzene ring modified paraffin comprises the following steps:
a1: detecting the mole number M of carboxyl in the acrylic acid modified paraffin wax in the step (1)1: and (2) placing the acrylic acid modified paraffin obtained by the reaction in the step (1) into a conical flask which is added with dimethylbenzene in advance, heating to dissolve a sample, adding 5 drops of phenolphthalein indicator, and dripping the indicator with 0.01mol/L NaOH solution while the indicator is hot until the solution is changed from colorless to red, namely the end point. The molar number M of carboxyl groups is calculated by a multiplier of the volume and concentration of the NaOH solution consumed1；
A2: detecting the mole number of acrylic acid in the paraffin modified by the benzene ring in the step (2): repeating the acid-base titration method on the benzene ring modified paraffin wax obtained in the step (2), and testing the mole number M of carboxyl in the benzene ring modified paraffin wax2；
A3: calculating the mass fraction of benzene rings in the paraffin modified by the benzene rings: mass fraction of benzene ring ═ 78 (M)1-M2)×100]/m；
Wherein m is the amount (g) of paraffin wax added in the step (1); 78 is the molar mass of the benzene ring, (g/mol).
In this application, paraffin has a very good emulsifying action in addition to its solidifying action.
The applicant finds that, surprisingly, after the paraffin modified by the benzene ring is added, the weather resistance of the chalk is further improved, the toughness is enhanced, the chalk is moistureproof, and the dust generation amount is greatly reduced. The probable reason is presumed to be that after the paraffin modified by the benzene ring is added, the paraffin modified by the benzene ring interacts with active sites in the chitosan, the monoglyceride and the silicone oil to form a network structure around the titanium dioxide, and the benzene ring in the modified paraffin is embedded into the network structure to form a compact and compact protection effect, so that the generation of nascent oxygen on the titanium dioxide is effectively prevented; the formed compact network structure can limit the migration of small molecules, so that the dust-free chalk is kept in an initial state; in addition, the nonpolar groups on the outermost layer block the entrance of water molecules, so that the chalk can write smoothly even in a humid environment, has clear handwriting and is not broken. Particularly, when the mass fraction of benzene rings in the benzene ring modified paraffin is 5-30%, various performances of the chalk are optimal. The possible reasons are: when the mass fraction of the benzene ring is less than 5%, the formed network structure is relatively sparse; when the mass fraction of the benzene ring is more than 30%, the formed network structure is not uniform, resulting in non-uniformity of the prepared chalk.
The second aspect of the invention provides a preparation method of the dust-free chalk, which at least comprises the following steps:
s1, adding white oil and paraffin into a stirring container in sequence, stirring for 1-2 hours at a rotating speed of 1500-2500 rpm and a temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, silicone oil and an auxiliary agent into the stirring container in the step S1, stirring at the rotating speed of 1500-2500 rpm and the temperature of 80-100 ℃ for 1.5-2 hours;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
In the application, through the synergistic effect of each component, on the premise that the chalk meets the requirements of low dust amount and good weather resistance, the writing adhesive force is strong and weak, so that the writing is suitable for being easily erased, and the experience of a user is greatly improved.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art without departing from the spirit and scope of the invention described above.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
In examples and comparative examples, the preparation methods of the alkane-modified chitosan and the benzene ring-modified paraffin were as follows:
the preparation method of the alkane modified chitosan comprises the following steps:
1) adding 15mmol of chitosan into a mixed solution of 100mL of 0.2mol/L acetic acid aqueous solution and 80mL of absolute ethyl alcohol, and swelling the solution to form a transparent viscous liquid, wherein the pH value is 5-6;
2) adding 15mmol of aliphatic aldehyde-ethanol solution and excessive reducing agent sodium cyanoborohydride at 800rpm, and continuously stirring for reaction for 24 hours;
3) and after the reaction is finished, adjusting the pH value to be 7-8 by using NaOH, separating out solid particles, performing suction filtration, washing by using a mixed solvent of ethanol and water, and drying to obtain the alkane modified chitosan.
The preparation method of the benzene ring modified paraffin comprises the following preparation steps:
(1) adding 1g of paraffin and 0.2g of acrylic acid into a 250mL four-neck flask, heating, melting and stirring, adding 0.02g of initiator benzoyl peroxide, and then heating to 80 ℃ for reaction for 2 hours to obtain the acrylic acid modified paraffin.
(2) And (2) adding the acrylic acid modified paraffin wax obtained in the step (1) into 0.05-0.5 g of aniline and 1mg of zinc powder, heating to 80 ℃, reacting for 2-10 h, and performing suction filtration to obtain benzene ring modified paraffin wax.
Example 1
Embodiment 1 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is anatase titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 5 parts of alkane modified chitosan and 5 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 8 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Embodiment 1 provides a method for preparing dust-free chalk, which comprises the following steps:
s1, adding white oil and paraffin into a stirring container in sequence, stirring for 1 hour at the rotating speed of 2000 r/min and the temperature of 80 ℃;
s2, sequentially adding titanium dioxide, silicone oil and an auxiliary agent into the stirring container in the step S1, stirring for 1.5 hours at the rotating speed of 2000 rpm and the temperature of 80 ℃;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
Example 2
Embodiment 2 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is anatase titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 20 parts of alkane modified chitosan and 20 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 8 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 2 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 3
Embodiment 3 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is anatase titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 15 parts of alkane modified chitosan and 15 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 8 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 3 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 4
Embodiment 4 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 15 parts of alkane modified chitosan and 15 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 8 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 4 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 5
Embodiment 5 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 15 parts of alkane modified chitosan and 15 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 12 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 5 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 6
Embodiment 6 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 15 parts of alkane modified chitosan and 15 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 10 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 6 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 7
Embodiment 7 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 9 parts of alkane modified chitosan and 21 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 10 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 7 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 8
Embodiment 8 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin modified by benzene rings, and the mass fraction of the benzene rings in the paraffin modified by the benzene rings is 5%;
the auxiliary agent consists of 6 parts of alkane modified chitosan and 24 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 10 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 8 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 9
Embodiment 9 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin with a modified benzene ring, and the mass fraction of the benzene ring in the paraffin with the modified benzene ring is 30%;
the auxiliary agent consists of 6 parts of alkane modified chitosan and 24 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 10 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 9 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Example 10
Embodiment 10 provides a nano dust-free chalk, which comprises the following components in parts by weight:
wherein the titanium dioxide is rutile type titanium dioxide;
the white oil (model number: 15#) is purchased from Xinsu grease Co., Ltd in Wuxi city;
the silicone oil is hydroxyl silicone oil, the content of hydroxyl in the hydroxyl silicone oil is 2 wt%, and the hydroxyl silicone oil is purchased from Qingdao Xingsheng organosilicon new material company;
the paraffin is paraffin with a modified benzene ring, and the mass fraction of the benzene ring in the paraffin with the modified benzene ring is 20%;
the auxiliary agent consists of 6 parts of alkane modified chitosan and 24 parts of monoglyceride;
the alkane modified chitosan is straight-chain alkane modified chitosan with 10 carbon atoms;
the monoglyceride is palmitic acid glyceride.
Example 10 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 1
Comparative example 1 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the silicone oil is methyl silicone oil.
Comparative example 1 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 2
Comparative example 2 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the auxiliary agent is 30 parts of monoglyceride.
Comparative example 2 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 3
Comparative example 3 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the auxiliary agent comprises 6 parts of chitosan and 24 parts of monoglyceride.
Comparative example 3 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 4
Comparative example 4 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the paraffin-modified chitosan was a linear paraffin-modified chitosan having 5 carbon atoms.
Comparative example 4 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 5
Comparative example 5 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the paraffin-modified chitosan was a linear paraffin-modified chitosan having 14 carbon atoms.
Comparative example 5 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 6
Comparative example 6 provides a dust-free chalk, which comprises the same components and weight parts as example 10, except that the auxiliary agent is 30 parts of alkane modified chitosan.
Comparative example 6 provides a method for preparing dust-free chalk, which comprises the same steps as example 1.
Comparative example 7
Comparative example 7 provides a dust-free chalk, which comprises the same components and weight parts as those of example 10, except that the auxiliary agent consists of 24 parts of alkane-modified chitosan and 6 parts of monoglyceride.
Comparative example 7 provides a method for preparing a dust-free chalk, which comprises the same steps as example 1.
Comparative example 8
Comparative example 8 provides a dust-free chalk, which comprises the same components and in parts by weight as in example 10, except that the paraffin wax was unmodified.
Comparative example 8 provides a method for preparing a dust-free chalk, which comprises the same steps as example 1.
Performance testing
The dust-free chalks described in examples 1 to 10 and comparative examples 1 to 8 were subjected to a performance test.
And (3) fracture resistance test: fixing the chalk in the position 1cm away from the two ends, hanging the plastic bag in the air by using a line rope without elasticity in the middle position of the chalk length, adding nails with the length of 30mm into the bag until the chalk is broken, and counting the added nails. A total of 10 chalks were tested and then averaged. Unit: and (4) root.
Moisture absorption test: the chalk was left to stand in a container having a relative humidity of 50% for a period of 20 days, and then the percentage of weight increase before and after the standing was measured. A total of 10 chalks were tested and then averaged. Unit: % of the total weight of the composition.
And (3) testing the folding resistance after moisture absorption: the chalk was left in a container having a relative humidity of 50% for a period of 20 days and then tested for breaking resistance after moisture absorption according to the method for breaking resistance test described above. Unit: and (4) root.
Measuring the amount of generated dust: a paper groove which is 5cm wide and 3cm deep is arranged at a position which is about 2cm away from the bottom of a blackboard with the length of 2.5mm and is level with the bottom of the blackboard, the blackboard is divided into squares with the length of 4cm X4 cm, ancient poems 'quiet night thought' is written for five times, the sizes of the fonts are as full as possible, the test is completed by the same person, and each time one piece of chalk is tested, the chalk is rested for 10 minutes, and dust in the paper groove is collected and weighed. A total of 10 chalks were tested and then averaged. Unit: and (5) mg.
TABLE 1 test results of the dust-free chalk performance described in examples 1-10 and comparative examples 1-8
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (7)
1. An easy-to-wipe nano dust-free chalk is characterized by at least comprising the following components in parts by weight: 50-80 parts of titanium dioxide, 1-15 parts of white oil, 1-12 parts of silicone oil, 1-12 parts of paraffin and 10-40 parts of an auxiliary agent;
wherein the auxiliary agent consists of 20-50 wt% of alkane modified chitosan and 50-80 wt% of monoglyceride;
the silicone oil is hydroxyl silicone oil;
the paraffin is paraffin with a modified benzene ring;
the alkane modified chitosan is straight-chain alkane modified chitosan with 8-12 carbon atoms.
2. A dust-free chalk according to claim 1, wherein the titanium dioxide is rutile type titanium dioxide and/or anatase type titanium dioxide.
3. The dustless chalk of claim 1, wherein the alkane modified chitosan is a linear alkane modified chitosan with 10-12 carbon atoms.
4. A dust-free chalk as claimed in claim 1, wherein the auxiliary agent is composed of 20-30 wt% of alkane modified chitosan and 70-80 wt% of monoglyceride.
5. The dustless chalk of claim 1, wherein the monoglyceride is at least one of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
6. A non-dusting chalk according to claim 5, characterised in that the monoglyceride is glyceryl palmitate.
7. A method for preparing dust-free chalk according to any one of the claims 1 to 6, characterized by comprising at least the following steps:
s1, adding white oil and paraffin into a stirring container in sequence, stirring for 1-2 hours at a rotating speed of 1500-2500 rpm and a temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, silicone oil and an auxiliary agent into the stirring container in the step S1, stirring at the rotating speed of 1500-2500 rpm and the temperature of 80-100 ℃ for 1.5-2 hours;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
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| CN115247009B (en) * | 2022-06-28 | 2023-08-22 | 深圳市鸿合创新信息技术有限责任公司 | Chalk with glass surface easy to write, preparation method and application thereof |
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| CN1450128A (en) * | 2003-04-21 | 2003-10-22 | 王力 | Dust free chalk and preparation process thereof |
| DE10256108A1 (en) * | 2002-11-29 | 2004-06-17 | Faber-Castell Ag | Wax pencil lead for writing or cosmetic use with wax and oil components, has wax component predominantly comprising shellac wax to give improved properties at summer temperatures |
| WO2011143037A1 (en) * | 2010-05-12 | 2011-11-17 | Elevance Renewable Sciences, Inc. | Natural oil based marking compositions and their methods of making |
| CN102417763A (en) * | 2011-01-07 | 2012-04-18 | 谢立华 | Preparation method of environmentally-friendly easily-erasable liquid teaching writing ink and color paste used therein |
| CN109054505A (en) * | 2018-07-24 | 2018-12-21 | 裴文韬 | A kind of wear-resisting easy coloring colour pen core modified material |
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| DE10256108A1 (en) * | 2002-11-29 | 2004-06-17 | Faber-Castell Ag | Wax pencil lead for writing or cosmetic use with wax and oil components, has wax component predominantly comprising shellac wax to give improved properties at summer temperatures |
| CN1450128A (en) * | 2003-04-21 | 2003-10-22 | 王力 | Dust free chalk and preparation process thereof |
| WO2011143037A1 (en) * | 2010-05-12 | 2011-11-17 | Elevance Renewable Sciences, Inc. | Natural oil based marking compositions and their methods of making |
| CN102417763A (en) * | 2011-01-07 | 2012-04-18 | 谢立华 | Preparation method of environmentally-friendly easily-erasable liquid teaching writing ink and color paste used therein |
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