CN110003720B - High-hardness anti-slip nanometer dust-free chalk and preparation method thereof - Google Patents
High-hardness anti-slip nanometer dust-free chalk and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
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Abstract
The invention relates to the field of cultural and educational supplies and stationery supplies, in particular to high-hardness anti-slip nanometer dust-free chalk and a preparation method thereof. The invention discloses a high-hardness anti-slip nano dust-free chalk which comprises the following components in parts by weight: 60-90 parts of titanium dioxide and 10-50 parts of auxiliary agent; wherein the auxiliary agent consists of monoglyceride and alkyl glucoside.
Description
Technical Field
The invention relates to the field of cultural and educational supplies and stationery supplies, in particular to high-hardness anti-slip nanometer dust-free chalk and a preparation method thereof.
Background
Chalk is still very popular in some countries and regions as an important teaching tool. Producible by chalk teachingDiameter of raw air dynamics<10 μm Particles (PM)10) And<2.5 μm Particles (PM)2.5). These fine particles can be inhaled into the lower respiratory tract along with the human breath, especially PM2.5Are prone to deposit in the bronchioles and alveolar regions and may enter the blood circulation. Thus, the use of chalk may affect the health of teachers and students. Research shows that the short-term exposure of chalk dust in a classroom can influence the function of the pulmonary airway of a teacher; prolonged exposure may induce respiratory diseases.
The chalks on the domestic market can be divided into common chalks and dustless chalks. The common chalk generates more dust, the using amount is gradually reduced, and most of the common chalks sold on the market at present are dustless chalks. In the chalk classroom teaching process, writing and handwriting erasing can both produce chalk dust particles. The proportion of coarse particles in chalk dust generated by common chalks in the use process of a wooden blackboard is large, and the use of dust-free chalks can reduce the total particle quantity, but fine particles are increased more. A study in 2014 showed spanish classroom PM2.5The concentration is 28% higher than that of the outdoor PM, and the PM is in the classroom2.5The main components are cotton fiber, chalk particles and salicide of teacher and student clothes. Disclose PM in the classroom of the chalk teaching2.5The concentration increase contributes greatly. Research shows that PM is in classroom10The main sources of the chalk are erasing and writing of the chalk and activities of students in classrooms. Wherein PM after chalk erasure10The instantaneous concentration of the active ingredient reaches 100 mu g/m3. The density gradually decreases again as the chalk erasing activity stops.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-hardness anti-slip nano dust-free chalk which is characterized by comprising the following components in parts by weight: 60-90 parts of titanium dioxide and 10-50 parts of auxiliary agent;
wherein the auxiliary agent consists of monoglyceride and alkyl glucoside.
In a preferred embodiment, the auxiliary agent consists of 70 to 90 weight percent of monoglyceride and 10 to 30 weight percent of alkyl glycoside.
In a preferred embodiment, the adjuvant consists of 80% by weight of monoglyceride and 20% by weight of an alkyl glycoside.
In a preferred embodiment, the monoglyceride is at least one selected from the group consisting of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
In a preferable embodiment, the dust-free chalk further comprises 3-15 parts by weight of white oil, 1-10 parts by weight of silicone oil and 3-15 parts by weight of lubricant.
As a preferred embodiment, the lubricant is selected from at least one of paraffin wax, calcium stearate, pentaerythritol adipate, 1, 2-propylene glycol, zinc stearate, and glycerin.
As a preferred embodiment, the lubricant is paraffin wax and/or 1, 2-propanediol.
As a preferable embodiment, the weight ratio of the auxiliary agent to the silicone oil to the lubricant is (5-10): 1: (1-3).
As a preferable embodiment, the weight ratio of the auxiliary agent to the silicone oil to the lubricant is (5-10): 1: 2.
the second aspect of the invention provides a preparation method of the dust-free chalk, which at least comprises the following steps:
s1, sequentially adding the white oil and the lubricant into a stirring container, and uniformly stirring at the temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, an auxiliary agent and silicone oil into the stirring container in the step S1, and uniformly stirring at the temperature of 80-100 ℃;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
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 high-hardness anti-slip nano dust-free chalk which comprises the following components in parts by weight: 60-90 parts of titanium dioxide and 10-50 parts of auxiliary agent;
wherein the auxiliary agent consists of monoglyceride and alkyl glucoside.
As a preferred embodiment, the dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide and 45 parts of an auxiliary agent.
Titanium white powder
In the application, the titanium dioxide is a polycrystalline inorganic compound, and the main component is TiO2. The Applicant has found that said 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 applicant has found that 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 ℃, the plate-type titanium dioxide can be prepared by adopting alkyl titanium or sodium titanate and potassium hydroxide or sodium hydroxide as 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.
In one embodiment, the titanium dioxide is rutile titanium dioxide and/or anatase titanium dioxide.
As a preferred embodiment, the titanium dioxide is rutile type titanium dioxide.
In a preferred embodiment, the particle size of the rutile titanium dioxide is 50-500 nm.
Preferably, the particle size of the rutile titanium dioxide is 300-350 nm.
The titanium dioxide (model BR648) was purchased from Hebei Bofeng chemical Co., Ltd.
Auxiliary agent
In one embodiment, the adjuvant is selected from at least one of monoglycerides, alkyl glycosides, celluloses, polyoxyethylene polyoxypropylene ether block copolymers.
Examples of monoglycerides include, but are not limited to, glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate, glyceryl linolenate.
In a preferred embodiment, the monoglyceride is at least one selected from the group consisting of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
Examples of cellulose include, but are not limited to, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, methyl ethyl cellulose.
Examples of polyoxyethylene polyoxypropylene ether block copolymers include, but are not limited to, alkylphenol polyoxyethylene polyoxypropylene ether, isooctanol polyoxyethylene polyoxypropylene ether, allyl polyoxyethylene polyoxypropylene ether.
In a preferred embodiment, the adjuvant consists of monoglycerides and alkyl glycosides.
In the application, the titanium dioxide is a polycrystalline compound, particles of the titanium dioxide are regularly arranged, and the titanium dioxide has excellent thermal stability, covering power and whiteness. However, titanium dioxide can adsorb moisture in the air, and the surface of titanium dioxide is provided with hydroxyl groups, so that titanium dioxide is difficult to disperse in an oil phase system. The applicant finds that the dispersibility of the titanium dioxide can be improved by adding the auxiliary agent, and the possible reason is that the polar group on the auxiliary agent interacts with the titanium dioxide, and the nonpolar group is compatible with the oil phase system, so that the dispersibility of the titanium dioxide is improved. Particularly, when the auxiliary agent consists of monoglyceride and alkyl glycoside, the auxiliary agent is limited by the self structure, the monoglyceride and the alkyl glycoside have different degrees of freedom motion, on one hand, the monoglyceride rotates and continuously adjusts conformation through the self molecular chain structure to provide holes for the alkyl glycoside so that the glycoside moves and is adsorbed on the surface of the titanium dioxide, on the other hand, the auxiliary agent with different structures is combined on the surface of the titanium dioxide, the space on the titanium dioxide is fully utilized, and the stable coating effect is formed on the titanium dioxide.
In a preferred embodiment, the auxiliary agent consists of 70 to 90 weight percent of monoglyceride and 10 to 30 weight percent of alkyl glycoside.
In a preferred embodiment, the adjuvant consists of 80% by weight of monoglyceride and 20% by weight of an alkyl glycoside.
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 a hydrophilic hydroxyl group, and has good surface activity.
As a preferred embodiment, the monoglyceride is glyceryl stearate.
The alkyl glycoside has a structural formula (1) as follows, R is C8-C14 alkyl, and m is polymerization degree and is 1-1.8.
In a preferred embodiment, the alkyl glycoside is at least one member selected from the group consisting of n-octyl glycoside, n-decyl glycoside, n-nonyl glycoside, n-undecyl glycoside, and n-dodecyl glycoside.
Preferably, the alkyl glycoside is selected from at least one of n-decyl glycoside, n-undecyl glycoside, and n-dodecyl glycoside.
More preferably, the alkyl glycoside is n-undecyl glycoside.
The preparation method of the alkyl glycoside comprises the following steps:
(1) adding 6mol of alcohol and 1mol of glucose into a four-neck flask with a reflux condensing device, a thermometer, a stirrer and a vacuum system, heating to 110 ℃, adding a certain amount of p-toluenesulfonic acid after uniformly stirring, and controlling the pressure to be 3-4 kPa;
(2) and after reacting for 2-8 h, cooling the solution to 60 ℃, adding a 5% sodium hydroxide solution under normal pressure, neutralizing the solution until the pH value is 8, filtering to remove low-polymerization sugar, carrying out vacuum distillation to remove excessive alcohol in the reaction, and then extracting and separating the residual alcohol by using a solvent to obtain the low-polymerization sugar-free alcohol.
Wherein, the alcohol in the step (1) is selected from one of n-octanol, n-decanol, n-nonanol glycoside, n-undecanol and n-dodecanol.
The weight of the p-toluenesulfonic acid in the step (1) is 1% of the sum of the weight of the alcohol and the weight of the glucose.
The applicant has unexpectedly found that the monoglyceride, which is glyceryl stearate, and the alkyl glycoside selected from at least one of n-decyl glycoside, n-undecyl glycoside, and n-dodecyl glycoside, improve the hardness of the chalk and the smoothness of the surface of the chalk. The possible reason is guessed that the alkyl glycoside is composed of a cyclic structure and a non-polar long chain, the non-polar chain on the alkyl glycoside and the non-polar chain on the monoglyceride have fluidity, a smooth film can be formed on the surface of the titanium dioxide, and meanwhile, the cyclic structure on the alkyl glycoside is used as an anchor point and is distributed at different positions of the film, so that the hardness of the chalk is increased. If the nonpolar chain of the monoglyceride or alkylglycoside is longer or shorter, this may affect the smoothness of the chalk and even lead to a decrease in the hardness of the chalk due to uneven distribution of the cyclic groups.
In a preferable embodiment, the dust-free chalk further comprises 3-15 parts by weight of white oil, 1-10 parts by weight of silicone oil and 3-15 parts by weight of lubricant.
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 is prepared from high-boiling fraction (lubricating oil fraction) of petroleum fractionation by dewaxing, carbonization, neutralization, and activated clay refining.
In the application, the basic composition of the white oil is a saturated hydrocarbon structure, the main component of the white oil is a mixture of normal isoparaffin of C16-C31, and substances such as aromatic hydrocarbon, nitrogen, oxygen, sulfur and the like are approximately zero.
The applicant finds that the white oil has good oxidation stability, chemical stability and light stability.
In a preferred embodiment, the kinematic viscosity of the white oil is 5 to 50mm2/s。
Preferably, the kinematic viscosity of the white oil is 5-12 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 10#) was purchased from Nissu oil Co., Ltd, Wuxi.
Silicone oil
In the present application, the silicone oil refers to a linear polysiloxane product that remains in a liquid state at room temperature.
In one embodiment, the silicone oil is at least one selected from the group consisting of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy phenyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil, cyanide-containing silicone oil, and hydroxy phenyl silicone oil.
As a preferred embodiment, the silicone oil is methyl silicone oil and/or hydroxyphenyl silicone oil.
The applicant finds that the methyl silicone oil has good chemical stability, insulating property and hydrophobic property because all organic groups are methyl. The methyl silicone oil also has excellent heat resistance, electric insulation, weather resistance, hydrophobicity, physiological inertia and smaller surface tension, and also has low viscosity-temperature coefficient, higher compression resistance and 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.
The methyl silicone oil is prepared by adding water into dimethyldichlorosilane to hydrolyze to prepare a primary condensed ring body, cracking and rectifying the ring body to prepare a low ring body, putting the ring body, a sealing agent and a catalyst together to perform telomerization to obtain a mixture with various polymerization degrees, and removing low-boiling-point substances through reduced pressure distillation.
Preferably, the silicone oil is a hydroxyphenyl silicone oil.
The preparation method of the hydroxyphenyl silicone oil comprises the following steps:
(1) mixing 0.04mol of diphenyl silanediol, 0.08mol of pyridine and 20g of THF in a 250mL single-neck bottle under the protection of nitrogen, and heating to 40 ℃;
(2) and (2) dropwise adding a mixture consisting of 1-10 g of dimethyldichlorosilane and 20.0g of THF into the mixture in the step (1), and continuing the reaction for 6 hours after the dropwise addition is finished.
(3) After most of low boiling point compounds are removed from the reaction mixture through pressure reduction, centrifugation, pressure reduction and other post-treatments, the pyridinium solvent and byproducts are obtained, and the hydroxyphenyl silicone oil is obtained.
In a preferred embodiment, the mass fraction of hydroxyl groups in the hydroxyphenyl silicone oil is 1 to 10%.
Preferably, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 3%.
In the application, the method for determining the mass fraction of hydroxyl in the hydroxyphenyl silicone oil comprises the following steps: weighing 1g of hydroxyphenyl silicone oil into a 250mL iodine flask, adding 10.0mL of toluene to dissolve, transferring 25.0mL of 0.5mol/L2, 4-toluene diisocyanate toluene solution and 1mL of 1% catalyst N, N-dimethylcyclohexylamine toluene solution into the toluene solution by a transfer pipette, covering the solution tightly, shaking the solution evenly, and standing the solution 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 mass fraction of hydroxyl groups is calculated as follows:
m(-OH)＝[c×(V1-V0)×17.01]×100/[m×1000]；
wherein m is the mass (g) of the hydroxyphenyl 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.
In the application, the silicone oil plays a role in demoulding and dispersing. The applicant finds that silicon-oxygen bonds in the silicone oil are weak dipoles, and silicone oil molecules adopt a specific extended chain configuration to spread on the surface of a mould to form a single-orientation arrangement, so that chalk demoulding is facilitated. The applicant also finds that when the silicone oil is hydroxyphenyl silicone oil, the weather resistance of the chalk is also improved; the possible reason is that the hydroxyphenyl silicone oil interacts with active sites in the auxiliary agent to form a network structure around the titanium dioxide, and benzene rings in the hydroxyphenyl silicone oil are embedded into the network structure to form a compact and compact protective effect, so that the generation of nascent oxygen on the titanium dioxide is effectively prevented; 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.
Lubricant agent
As a preferred embodiment, the lubricant is selected from at least one of paraffin wax, calcium stearate, pentaerythritol adipate, 1, 2-propylene glycol, zinc stearate, and glycerin.
As a preferred embodiment, the lubricant is paraffin wax and/or 1, 2-propanediol.
Preferably, the lubricant is paraffin wax and 1, 2-propylene glycol.
In the present application, the lubricant can reduce the friction coefficient between inorganic particles and reduce the cohesion between organic substances. The applicant has found that when the lubricant is paraffin wax and 1, 2-propanediol, the toughness of the chalk is improved. The possible reasons are: the assistant and the hydroxyphenyl silicone oil contain rigid groups and long chains, different pores can be formed between the rigid groups and the rigid groups, between the rigid groups and the long chains, and small molecular substances in the lubricant are embedded between the pores, so that the movement between chain segments is reduced, a bridge is formed between the rigid groups, a more perfect three-dimensional structure is formed around the titanium dioxide, and the toughness of the chalk is improved.
Preferably, the weight part ratio of the paraffin wax to the 1, 2-propylene glycol in the lubricant is (4-8): 1.
more preferably, the weight ratio of the paraffin wax to the 1, 2-propylene glycol in the lubricant is 6: 1.
the paraffin is a hydrocarbon mixture with 18-30 carbon atoms, and the main components are straight-chain paraffin (about 80-95%), and a small amount of paraffin with individual branch chains and monocyclic naphthene with long side chains (the total content of the two is less than 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, and squeezing and dewaxing the lubricating oil fraction to prepare a cerate, deoiling the cerate and supplementing and refining the cerate.
Herein, the paraffin wax is selected from at least one of microcrystalline wax, liquid paraffin wax, and polyethylene wax.
The microcrystalline wax is a mineral wax with high molecular weight and high melting point, and has higher branched alkane and cyclic alkane. The microcrystalline wax has good toughness and low permeability to water vapor. The solid is colorless to white massive solid at normal temperature, is odorless and tasteless, and has a melting point of 60-85 ℃.
The liquid paraffin is paraffin containing normal paraffin obtained by using kerosene or diesel oil fraction as a raw material and performing adsorption separation by a molecular sieve or dewaxing by isopropanol-urea; or liquid paraffin synthesized in the coal/natural gas liquefaction process.
The polyethylene wax refers to low molecular weight polyethylene with molecular weight of 1500-25000 or partially oxidized low molecular weight polyethylene. It is in the form of granule, white powder, block and milky wax. Has excellent flowability, electrical performance and demolding performance.
In a preferred embodiment, the paraffin wax is polyethylene wax.
The polyethylene wax (model: A-C6A) was purchased from Keye chemical industry.
As a preferable embodiment, the weight ratio of the auxiliary agent to the silicone oil to the lubricant is (5-10): 1: (1-3).
As a preferable embodiment, the weight ratio of the auxiliary agent to the silicone oil to the lubricant is (5-10): 1: 2.
preferably, the weight ratio of the auxiliary agent to the silicone oil to the lubricant is 9: 1: 2.
in the application, the auxiliary agent, the silicone oil and the lubricant act together to form a more perfect three-dimensional structure around the titanium dioxide, so that the chalk has moderate hardness, weather resistance and toughness. No matter one of the three components is too much or too little, the compactness and the shape of the network structure are damaged, and the performance of the chalk is deteriorated.
The second aspect of the invention provides a preparation method of the dust-free chalk, which at least comprises the following steps:
s1, sequentially adding the white oil and the lubricant into a stirring container, and uniformly stirring at the temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, an auxiliary agent and silicone oil into the stirring container in the step S1, and uniformly stirring at the temperature of 80-100 ℃;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 60 parts of titanium dioxide, 10 parts of an auxiliary agent, 3 parts of white oil, 1 part of silicone oil and 3 parts of a lubricant;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 70 wt% of monoglyceride and 30 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-decyl glycoside;
the preparation method of the n-decyl glucoside comprises the following steps:
(1) adding 6mol of n-decanol and 1mol of glucose into a four-neck flask with a reflux condensing device, a thermometer, a stirrer and a vacuum system, heating to 110 ℃, adding a certain amount of p-toluenesulfonic acid after uniformly stirring, and controlling the pressure to be 3 kPa-4 kPa;
(2) after 4h of reaction, the temperature of the solution is reduced to 60 ℃, 5 percent sodium hydroxide solution is added under normal pressure, the solution is neutralized to pH 8, low polymeric sugar is filtered and removed, vacuum distillation is carried out, excessive alcohol in the reaction is removed, and then residual alcohol is extracted and separated by adopting a solvent, thus obtaining the product.
The weight of the p-toluenesulfonic acid in the step (1) is 1% of the sum of the weight of the n-decanol and the weight of the glucose.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, and the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%.
The preparation method of the hydroxyphenyl silicone oil comprises the following steps:
(1) mixing 0.04mol of diphenyl silanediol, 0.08mol of pyridine and 20g of THF in a 250mL single-neck bottle under the protection of nitrogen, and heating to 40 ℃;
(2) a mixture of dimethyldichlorosilane, 20.0g THF was added dropwise to the mixture of step (1), and the reaction was continued for 6h after completion of the addition.
(3) After most of low boiling point compounds are removed from the reaction mixture through post-treatment such as decompression, centrifugation, decompression and the like, the pyridinium solvent and byproducts are obtained, and the hydroxyphenyl silicone oil with 1 percent of hydroxyl mass fraction is obtained.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The preparation method of the dust-free chalk comprises the following steps:
s1, adding the white oil and the lubricant into a stirring container in sequence, and stirring uniformly at the temperature of 80 ℃;
s2, sequentially adding titanium dioxide, an auxiliary agent and silicone oil into the stirring container in the step S1, and stirring uniformly at the temperature of 85 ℃;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
Example 2
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 90 parts of titanium dioxide, 50 parts of auxiliary agent, 15 parts of white oil, 10 parts of silicone oil and 15 parts of lubricant;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 70 wt% of monoglyceride and 30 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-decyl glycoside;
the preparation method of the n-decyl glucoside is the same as that of example 1.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 3
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 70 wt% of monoglyceride and 30 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-decyl glycoside;
the preparation method of the n-decyl glucoside is the same as that of example 1.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 4
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 90 wt% of monoglyceride and 10 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-decyl glycoside;
the preparation method of the n-decyl glucoside is the same as that of example 1.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 5
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-decyl glycoside;
the preparation method of the n-decyl glucoside is the same as that of example 1.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 6
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-dodecyl glycoside;
the preparation method of the n-dodecyl glucoside is the same as that of example 1, and the difference is that the alcohol is n-dodecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 7
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-undecyl glycoside;
the preparation method of the n-undecyl glycoside is the same as that in example 1, except that the alcohol is n-undecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 1%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 8
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-undecyl glycoside;
the preparation method of the n-undecyl glycoside is the same as that in example 1, except that the alcohol is n-undecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 10%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 9
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-undecyl glycoside;
the preparation method of the n-undecyl glycoside is the same as that in example 1, except that the alcohol is n-undecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 3%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (4): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 10
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-undecyl glycoside;
the preparation method of the n-undecyl glycoside is the same as that in example 1, except that the alcohol is n-undecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 3%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is (8): 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 11
A high-hardness anti-slip nano dust-free chalk comprises the following components in parts by weight: 75 parts of titanium dioxide, 35 parts of an auxiliary agent, 10 parts of white oil, 5 parts of silicone oil and 10 parts of a lubricating agent;
the titanium dioxide is rutile titanium dioxide, and is purchased from Hebei Bofeng chemical Co., Ltd, model BR 648.
The auxiliary agent consists of 80 wt% of monoglyceride and 20 wt% of alkyl glycoside, wherein the monoglyceride is glyceryl stearate, and the alkyl glycoside is n-undecyl glycoside;
the preparation method of the n-undecyl glycoside is the same as that in example 1, except that the alcohol is n-undecyl alcohol.
The white oil (model number: 10#) was purchased from Xinsu grease Co., Ltd.
The silicone oil is hydroxyphenyl silicone oil, the mass fraction of hydroxyl in the hydroxyphenyl silicone oil is 3%, and the preparation method of the hydroxyphenyl silicone oil is the same as that in example 1.
The lubricant is paraffin and 1, 2-propylene glycol, and the weight ratio of the paraffin to the 1, 2-propylene glycol is 6: 1, the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) is purchased from Keynin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 12
The specific components and the parts by weight of the high-hardness anti-skid nano dust-free chalk are the same as those of example 11, and the difference is that 45 parts of the auxiliary agent;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 13
The specific components and the parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those of example 12, and the difference is that the auxiliary agent is undecyl glucoside;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 14
The specific components and the parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those of example 12, and the difference is that the auxiliary agent is glyceryl stearate;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 15
The specific components and the parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those of example 12, and the difference is that the alkyl glycoside is n-tetradecyl glycoside;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 16
The specific components and the parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those of example 12, and the difference is that the alkyl glycoside is n-heptyl glycoside;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 17
The specific components and parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those in example 12, and the difference is that the silicone oil is phenyl silicone oil;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 18
The specific components and parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those in example 12, and the difference is that the lubricant is paraffin, the paraffin is polyethylene wax, and the polyethylene wax (type: A-C6A) is purchased from Keyin chemical industry.
The specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 19
The specific components and parts by weight of the high-hardness anti-slip nano dust-free chalk are the same as those of example 12, except that the lubricant is 1, 2-propylene glycol;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Example 20
The specific components and the parts by weight of the high-hardness anti-skid nano dust-free chalk are the same as those of example 12, and the difference is that 10 parts of the auxiliary agent is used;
the specific steps of the preparation method of the dust-free chalk are the same as those of the example 1.
Performance testing
The dust-free chalks described in the examples 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.
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 for the performance of the dust free chalk described in the examples
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 (6)
1. The high-hardness anti-slip nano dust-free chalk is characterized by comprising the following components in parts by weight: 60-90 parts of titanium dioxide, 10-50 parts of an auxiliary agent, 3-15 parts of white oil, 1-10 parts of silicone oil and 3-15 parts of a lubricant;
wherein the auxiliary agent consists of monoglyceride and alkyl glucoside; the alkyl glycoside is selected from one of n-decyl glycoside, n-undecyl glycoside and n-dodecyl glycoside;
the lubricant is paraffin and 1, 2-propylene glycol; the silicone oil is hydroxyphenyl silicone oil;
the auxiliary agent, the silicone oil and the lubricant are in a weight ratio of (5-10): 1: (1-3).
2. The dust-free chalk of claim 1, wherein the assistant is composed of 70-90 wt% of monoglyceride and 10-30 wt% of alkyl glycoside.
3. The chalk of claim 2, wherein the adjuvant is composed of 80% by weight of monoglyceride and 20% by weight of an alkyl glycoside.
4. The chalk of claim 1, wherein said monoglyceride is at least one member selected from the group consisting of glyceryl oleate, glyceryl linoleate, glyceryl palmitate, glyceryl behenate, glyceryl stearate, glyceryl laurate and glyceryl linolenate.
5. The dust-free chalk of claim 1, wherein the weight ratio of the auxiliary agent, the silicone oil and the lubricant is (5-10): 1: 2.
6. a method for preparing dust-free chalk according to any one of the claims 1-5, characterized by comprising at least the following steps:
s1, sequentially adding the white oil and the lubricant into a stirring container, and uniformly stirring at the temperature of 70-100 ℃;
s2, sequentially adding titanium dioxide, an auxiliary agent and silicone oil into the stirring container in the step S1, and uniformly stirring at the temperature of 80-100 ℃;
s3, injecting the mixture obtained in the step S2 into a mold, pressing, cooling, cutting into finished products, and packaging.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101550301A (en) * | 2009-05-23 | 2009-10-07 | 曾爱军 | Biochemical chalk and preparation method thereof |
| WO2011143037A1 (en) * | 2010-05-12 | 2011-11-17 | Elevance Renewable Sciences, Inc. | Natural oil based marking compositions and their methods of making |
| CN108129915A (en) * | 2017-12-28 | 2018-06-08 | 南京工程学院 | Chalk dust recycles production technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550301A (en) * | 2009-05-23 | 2009-10-07 | 曾爱军 | Biochemical chalk and preparation method thereof |
| WO2011143037A1 (en) * | 2010-05-12 | 2011-11-17 | Elevance Renewable Sciences, Inc. | Natural oil based marking compositions and their methods of making |
| CN108129915A (en) * | 2017-12-28 | 2018-06-08 | 南京工程学院 | Chalk dust recycles production technology |
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