CN110003720A - 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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- CN110003720A CN110003720A CN201910138660.9A CN201910138660A CN110003720A CN 110003720 A CN110003720 A CN 110003720A CN 201910138660 A CN201910138660 A CN 201910138660A CN 110003720 A CN110003720 A CN 110003720A
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- C—CHEMISTRY; METALLURGY
- 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 present invention relates to school supply and stationery and stationery fields, and in particular to a kind of high rigidity antiskid nanometer dust-free chalk and
Preparation method.
Background technique
For chalk as a kind of important educational aid, the use in some countries and regions is still very universal.Chalk religion
Learn the particle (PM that can produce aerodynamic diameter < 10 μm10) and < 2.5 μm of particle (PM2.5).These tiny particulate matters can
As human body respiration sucks lower respiratory tract, especially PM2.5It is easy to be deposited on bronchiole and alveolar region, and possibly into blood
Liquid circulation.Therefore, the use of chalk may influence the health of Faculty and Students.Studies have shown that the exposure meeting in short term of classroom chalk dust
Influence teacher's lung airway function；Long-term exposure then may induce respiratory disease.
Chalk on domestic market can be divided into common chalk and dust-free chalk.Common chalk makes because generating more dust
Dosage gradually decreases, and what is sold currently on the market is mostly dust-free chalk.During chalk classroom instruction, writes and writing is wiped
Chalk dust particle can be generated.The chalk dust that common chalk generates in wooden blackboard use process, coarse granule proportion compared with
Greatly, although and dust-free chalk use can reduce total particle quantity, fine particle but increases more.A Xiang Yan in 2014
Study carefully data and shows Spain classroom PM2.5Concentration is higher than outdoor concentration 28%, and PM in classroom2.5Main component is Faculty and Students
Clothes cotton fiber, chalk particulate matter and Gui hydrochlorate etc..Chalk teaching is disclosed to PM in classroom2.5Concentration increase has very big tribute
It offers.Some researches show that PM in classroom10Main source be chalk activity of the erasable and student in classroom.Wherein, chalk is wiped
PM afterwards10Instantaneous concentration reach 100 μ g/m3.With the erasable movable stopping of chalk, concentration gradually decreases again.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of high rigidity antiskid nanometer without dirt powder
Pen, which is characterized in that by weight, including following components: 60-90 parts of titanium dioxide, 10-50 parts of auxiliary agent；
Wherein, the auxiliary agent is made of monoglyceride and alkyl glycosides.
As a preferred embodiment, the auxiliary agent by weight percent be 70~90% monoglyceride and 10~
30% alkyl glycosides composition.
As a preferred embodiment, the auxiliary agent is 80% monoglyceride and 20% alkyl by weight percent
Glucosides composition.
As a preferred embodiment, the monoglyceride is sweet selected from olein, glyceryl linoleate, palmitinic acid
At least one of grease, Compritol 888 ATO, tristerin, glyceryl laurate ester, glyceryl linolenate.
As a preferred embodiment, by weight, the dust-free chalk further includes 3-15 parts of white oil, silicone oil 1
~10 parts, 3~15 parts of lubricant.
As a preferred embodiment, the lubricant be selected from paraffin, calcium stearate, stearic acid pentaerythritol ester,
At least one of adipic acid pentaerythritol ester, 1,2- propylene glycol, zinc stearate, glycerol.
As a preferred embodiment, the lubricant is paraffin and/or 1,2-PD.
As a preferred embodiment, the weight part ratio of the auxiliary agent, silicone oil, lubricant is (5~10): 1:(1~
3)。
As a preferred embodiment, the weight part ratio of the auxiliary agent, silicone oil, lubricant is (5~10): 1:2.
The second aspect of the present invention provides the preparation method of the dust-free chalk, at least includes the following steps:
S1 sequentially adds white oil, lubricant in stirring container, at 70~100 DEG C of temperature, stirs evenly；
S2 sequentially adds titanium dioxide, auxiliary agent, silicone oil in the stirring container of step S1, and at 80~100 DEG C of temperature, stirring is equal
It is even；
S3 by step S2 mixture injection mold, compacting, cooling, be cut into finished product, packaging, to obtain the final product.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
For the purpose of following detailed description, it should be understood that the present invention can be used various substitutions variation and step it is suitable
Sequence, unless specifically stated on the contrary.In addition, being indicated in the case where in addition in any operational instances or otherwise pointing out
Such as all numbers of the amount of ingredient used in description and claims should be understood in all cases by term
" about " it modifies.Therefore, unless indicated to the contrary, the numerical parameter otherwise illustrated in the following description and appended dependent claims is root
The approximation changed according to the expected performance of the invention to be obtained.It is at least not intended to for the applicable of doctrine of equivalents being limited in
In the scope of the claims, each numerical parameter should at least be given up according to the number of the effective digital of report and by the way that application is common
Enter technology to explain.
Although illustrating that broad range of numberical range and parameter of the invention are approximations, listed in specific example
Numerical value is reported as accurately as possible.However, any numerical value inherently includes the standard deviation by finding in its each self-test measurement
The certain errors necessarily led to.
When a numberical range disclosed herein, above range is considered as continuously, and the minimum value including the range and most
Big value and each value between this minimum value and maximum value.Further, when range refers to integer, including the model
Each integer between minimum value and maximum value enclosed.In addition, when providing multiple range Expressive Features or characteristic, Ke Yihe
And the range.In other words, unless otherwise specified, otherwise all ranges disclosed herein are understood to include and are wherein included into
Any and all subrange.For example, should be regarded as including between minimum value 1 and maximum value 10 from the specified range of " 1 to 10 "
Any and all subrange.The Exemplary range of range 1 to 10 include but is not limited to 1 to 6.1,3.5 to 7.8,5.5 to
10 etc..
To solve the above-mentioned problems, the present invention provides a kind of high rigidity antiskid nanometer dust-free chalks, by weight, packet
Include following components: 60-90 parts of titanium dioxide, 10-50 parts of auxiliary agent；
Wherein, the auxiliary agent is made of monoglyceride and alkyl glycosides.
As a preferred embodiment, the dust-free chalk, by weight, including following components: titanium dioxide 75
Part, 45 parts of auxiliary agent.
Titanium dioxide
In the application, the titanium dioxide is a kind of polymorphic inorganic compound, main component TiO2.Applicants have discovered that
The TiO2It is a kind of polycrystalline compounds, particle is in regularly arranged.Its chemical property is extremely stable, is the two of a kind of slant acidity
Property oxide.It is hardly reacted with other elements and compound under room temperature, to oxygen, ammonia, nitrogen, hydrogen sulfide, carbon dioxide, titanium dioxide
Sulphur does not all work, not soluble in water, fatty, is also insoluble in diluted acid and inorganic acid, alkali, is dissolved only in hydrofluoric acid.Under light action, titanium
Continuous redox reaction can occur for white powder, have photochemical activity.
Titanium dioxide in the application can be prepared by sulfuric acid process.The sulfuric acid process refers to using sulfuric acid as production titanium dioxide
Primary raw material first has to obtain titanium sulfate solution, through restoring the most of impurity ferro element removed in solution with vacuum crystallization；It is logical
It crosses and titanium liquid is heated to temperature close to boiling, hydrolyze titanium sulfate solution, obtain metatitanic acid precipitating；Metatitanic acid was precipitated
Filter, removes most spent acid and harmful metal impurity；Again through one to secondary washing, most impurity gold in metatitanic acid are removed
Belong to element；Salt treatment agent appropriate is added into metatitanic acid, and after filtering and removing major part water, metatitanic acid filter cake enters brickkiln and forges
It burns, obtains titanium dioxide first product.After post treatment by the above first product, titanium dioxide product is obtained.
Titanium dioxide in the application can also be prepared by chloridising.The chloridising is the side using chlorine as primary raw material
Method.The ferro element in ilmenite first is removed with hydrochloric acid or smelting, obtains the very high titanium material of Ti content；Then by coke and chlorine
It reacts with titanium material and generates titanium tetrachloride；After heated purification, react to obtain rutile titanium dioxide at high temperature with oxygen
Powder first product.The above first product after post treatment, obtains rutile type titanium white product.
Applicants have discovered that there are three types of crystal habits for titanium dioxide tool, it is rutile type titanium white, anatase thpe white powder respectively
With plate state type titanium dioxide.Wherein, plate state type titanium dioxide is a kind of highly unstable crystal form, belongs to orthorhombic system, lattice is by 8
Unit TiO2Composition.When temperature rises to 650 DEG C or so, plate state type titanium dioxide translates into rutile type titanium white.200~
At a temperature of 600 DEG C, uses alkyl titanium or sodium titanate and potassium hydroxide or sodium hydroxide for raw material, plate state type titanium dioxide can be made.
Anatase thpe white powder is square crystallographic system, and lattice is by 4 unit TiO2Composition, the angle of diffraction is 25.5 degree, shape approximate regulation
It is octahedra.Rutile type titanium white is square crystallographic system, and lattice is by 2 unit TiO2Composition, the angle of diffraction is 27.5 degree, crystal
It carefully grows, shape assumes diamond in shape.
In one embodiment, the titanium dioxide is rutile type titanium white and/or anatase thpe white powder.
As a preferred embodiment, the titanium dioxide is rutile type titanium white.
As a preferred embodiment, the partial size of the rutile type titanium white is 50~500nm.
Preferably, the partial size of the rutile type titanium white is 300~350nm.
Titanium dioxide (model BR648) purchase is in Hebei Bo Feng Chemical Co., Ltd..
Auxiliary agent
In one embodiment, the auxiliary agent is selected from monoglyceride, alkyl glycosides, cellulose, polyoxyethylene polyoxypropylene
At least one of ether block copolymers.
As the example of monoglyceride, including but not limited to olein, glyceryl linoleate, tripalmitin, mountain
Yu acid glyceride, tristerin, glyceryl laurate ester, glyceryl linolenate.
As a preferred embodiment, the monoglyceride is sweet selected from olein, glyceryl linoleate, palmitinic acid
At least one of grease, Compritol 888 ATO, tristerin, glyceryl laurate ester, glyceryl linolenate.
As the example of cellulose, including but not limited to methylcellulose, ethyl cellulose, carboxymethyl cellulose, methyl
Ethyl cellulose.
As the example of polyoxyethylene poly-oxygen propylene aether block copolymer, including but not limited to alkylphenol-polyethenoxy polyoxy
Propylene ether, isooctanol polyoxyethylene poly-oxygen propylene aether, allyl polyethenoxy polyethenoxy ether.
In a preferred embodiment, the auxiliary agent is made of monoglyceride and alkyl glycosides.
In the application, the titanium dioxide is polycrystalline compounds, its particle in regularly arranged, have excellent thermal stability,
Covering power and whiteness.But the moisture in air can be adsorbed due to titanium dioxide, surface has hydroxyl, it is difficult to be scattered in oil-based system
In.Applicants have discovered that auxiliary agent, which is added, can be improved the dispersibility of titanium dioxide, the possible reason is the polar group on the auxiliary agent
Group interacts with titanium dioxide, and nonpolar group is compatible with oil-based system, to improve the dispersibility of titanium dioxide.Especially institute
When stating auxiliary agent and being made of monoglyceride and alkyl glycosides, it is limited to self structure, monoglyceride and alkyl glycosides have different freedom
Degrees of motion, one side monoglyceride provide hole by rotation in self-molecules present chain structure and continuous adjustment conformation for alkyl glycosides
Keep glucosides mobile and be adsorbed on the surface of titanium dioxide, the auxiliary agent of another aspect different structure is incorporated in titanium dioxide surface, sufficiently benefit
With the space on titanium dioxide, stable coating function is formed to titanium dioxide.
As a preferred embodiment, the auxiliary agent by weight percent be 70~90% monoglyceride and 10~
30% alkyl glycosides composition.
As a preferred embodiment, the auxiliary agent is 80% monoglyceride and 20% alkyl by weight percent
Glucosides composition.
In the application, term " monoglyceride " is mono fatty acid glyceride.
In the application, the mono fatty acid glyceride contains the chain alkyl and hydrophilic hydroxyl of an oleophylic, has good
Good surface-active.
As a preferred embodiment, the monoglyceride is tristerin.
The structural formula (1) of the alkyl glycosides is as follows, and R is the alkyl of C8-C14, and m refers to the degree of polymerization, is 1~1.8.
As a preferred embodiment, the alkyl glycosides is selected from Octyl glucoside, positive decyl glucosides, n-nonyl sugar
At least one of glycosides, n-undecane base glucosides, n-dodecyl polyglucoside.
Preferably, the alkyl glycosides in positive decyl glucosides, n-undecane base glucosides, n-dodecyl polyglucoside extremely
Few one kind.
The undecyl glucosides it is highly preferred that the alkyl glycosides is positive.
The preparation method of the alkyl glycosides, comprising the following steps:
(1) 6mol alcohol, 1mol glucose are added with reflux condensate device, thermometer, blender and vacuum system
In four-hole boiling flask, heat to 110 DEG C, it is to be mixed uniformly after, be added a certain amount of p-methyl benzenesulfonic acid, control pressure 3kPa~
4kPa；
(2) after reacting 2~8h, solution temperature is down to 60 DEG C, under normal pressure, 5% sodium hydroxide solution is added, it will be molten
Liquid is neutralized to pH=8, is removed by filtration oligomerization sugar, and vacuum distillation then will be remaining using solvent except excessive alcohol in dereaction
Alcohol extraction and separation come out to get.
Wherein, alcohol described in step (1) is in n-octyl alcohol, Decanol, n-nonyl alcohol glycosides, positive undecyl alcohol, n-dodecanol
It is a kind of.
The weight of p-methyl benzenesulfonic acid is the 1% of the sum of alcohol and glucose weight in step (1).
The applicant has been surprisingly found that, the monoglyceride is tristerin, the alkyl glycosides be selected from positive decyl glucosides,
When at least one of n-undecane base glucosides, n-dodecyl polyglucoside, hardness and the chalk surface of chalk can be improved
Smoothness.Conjecture is non-in alkyl glycosides the possible reason is the alkyl glycosides is made of cyclic structure and nonpolar long-chain
Apolar chain in polar chain and monoglyceride has mobility, and smooth film, while alkyl sugar can be formed on titanium dioxide surface
Cyclic structure on glycosides is distributed in the different location of film, increases the hardness of chalk as anchor point.If monoglyceride or alkyl glycosides
Apolar chain it is longer or shorter when, can all influence the smoothness of chalk even since being unevenly distributed for cyclic group causes
The decline of chalk hardness.
As a preferred embodiment, by weight, the dust-free chalk further includes 3-15 parts of white oil, silicone oil 1
~10 parts, 3~15 parts of lubricant.
White oil
White oil, also known as paraffin oil, mineral oil, colourless, tasteless, chemical inertness, light stability can be good.
The white oil is from the high boiling fraction (i.e. lube cut) of petroleum fractionating through dewaxing, carbonization, neutralization, atlapulgite
It is formed after the processing such as purification.
In the application, the white oil basic composition is saturated hydrocarbon structure, and main component is the positive isomeric alkane of C16~C31
The mixture of hydrocarbon, the substances such as aromatic hydrocarbon, nitrogenous, oxygen, sulphur are similar to zero.
Applicants have discovered that the white oil has good oxidation stability, chemical stability, light stability.
In a preferred embodiment, the dynamic viscosity of the white oil is 5~50mm2/s。
Preferably, the dynamic viscosity of the white oil is 5~12mm2/s。
In the application, the dynamic viscosity of white oil is measured with reference to the method for GB/T265-1988.Determination step be at 40 DEG C,
The white oil of certain volume flows through the time for the glass capillary viscometer that one has been demarcated under gravity, and the capillary of viscosmeter is normal
The products with flowing time are counted, the dynamic viscosity of white oil at as 40 DEG C.
In the application, white oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
Silicone oil
In the application, the silicone oil refers to the linear polysiloxanes product for keeping liquid condition at room temperature.
In one embodiment, the silicone oil is selected from methyl-silicone oil, methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, methyl
Containing hydrogen silicone oil, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, ethylene methacrylic
Base silicone oil, methylhydroxy phenyl silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil, containing in nitrile silicone, hydroxy phenyl silicone oil extremely
Few one kind.
As a preferred embodiment, the silicone oil is methyl-silicone oil and/or hydroxy phenyl silicone oil.
Applicants have discovered that the methyl-silicone oil has good chemical stabilization because of all methyl of its organic group
Property, insulating properties, hydrophobic performance are good.The methyl-silicone oil also has brilliant heat resistance, electrical insulating property, weatherability, hydrophobicity, life
Inertia and lesser surface tension are managed, additionally there is low viscosity-temperature coefficient, higher resistance to compression, also there is radiation-resistant property
Energy.The silicone oil there are many property, such as it is anti-oxidant, flash-point is high, volatility is small, corrosion-free to metal, nontoxic.
The methyl-silicone oil of the application be added by dimethyldichlorosilane water hydrolyze be made first minification polycyclic body, ring body through cracking,
Low ring body is made in rectifying, and the mixed of various different polymerization degrees just then can be obtained in the telomerization of putting together of ring body, closure agent, catalyst
Object is closed, removing low-boiling-point substance through vacuum distillation can be made.
Preferably, the silicone oil is hydroxy phenyl silicone oil.
The preparation method of the hydroxy phenyl silicone oil, comprising the following steps:
(1) under nitrogen protection atmosphere, 0.04mol diphenyl silanediol, 0.08mol pyridine and 20gTHF are mixed in
40 DEG C are warming up in 250mL single port bottle and by temperature；
(2) by the dimethyldichlorosilane of 1~10g, the mixed of step (1) is added dropwise in the mixture of 20.0g THF composition
It closes in object, the reaction was continued 6h after being added dropwise to complete.
(3) reaction mixture is after the post-processings such as decompression, centrifugation and decompression remove most of low-boiling compound,
Pyridine salt solvent and by-product are to get hydroxy phenyl silicone oil.
In a preferred embodiment, the mass fraction of hydroxyl is 1~10% in the hydroxy phenyl silicone oil.
Preferably, the mass fraction of hydroxyl is 3% in the hydroxy phenyl silicone oil.
In the application, the measuring method of hydroxyl mass fraction in hydroxy phenyl silicone oil are as follows: weigh 1g hydroxy phenyl silicone oil in
In 250mL iodine flask, the dissolution of 10.0mL toluene is added, pipettes 25.0ml 0.5mol/L2,4- toluene diisocynate with pipette
1% catalyst n of ester toluene solution and 1mL, N- dimethyl cyclohexyl amine toluene solution are covered tightly and are shaken up in wherein, place 10min.Again
25.0mL 1.00mol/L diethylamide toluene solution is added, covers tightly and shakes up, after placing 10min, adds 20mL isopropanol and 1~2
Bromocresol green indicator solution is dripped, is titrated to until blue sports yellow with 0.50mol/L hydrochloric acid standard solution.Sky is done simultaneously
White test.The mass fraction of hydroxyl is calculated as follows:
M (- OH)=[c × (V1-V0)×17.01]×100/[m×1000]；
Wherein, m is the quality (g) of hydroxy phenyl silicone oil；
C is the concentration (mol/L) of hydrochloric acid standard solution；
V1For the volume (mL) of sample consumption hydrochloric acid standard solution；
V0The volume (mL) of hydrochloric acid standard solution is consumed for blank sample.
In the application, the silicone oil plays the role of demoulding, dispersing agent.Applicants have discovered that the silicon oxygen in the silicone oil
Key is weak dipole, and the silicone molecule is taken distinctive stretching, extension chain configuration to sprawl into mono-oriented in die surface and arranged, is easy to
Chalk demoulding.Applicant have also found that also improving the weatherability of chalk when the silicone oil is hydroxy phenyl silicone oil；It is possible
The reason is that the active site in the hydroxy phenyl silicone oil and auxiliary agent interacts, network structure, hydroxyl are formed around titanium dioxide
In phenyl ring embedded network structure in base phenyl silicone oil, fine and close compact protective effect is formd, it is highly effective to prevent titanium
The generation of nascent oxygen on white powder；In addition, outermost non-polar group hinders the entrance of hydrone, even if making chalk in tide
Under wet environment, also can fluent writing, clear writing do not fracture.
Lubricant
As a preferred embodiment, the lubricant be selected from paraffin, calcium stearate, stearic acid pentaerythritol ester,
At least one of adipic acid pentaerythritol ester, 1,2- propylene glycol, zinc stearate, glycerol.
As a preferred embodiment, the lubricant is paraffin and/or 1,2-PD.
Preferably, the lubricant is paraffin and 1,2-PD.
In the application, the lubricant can reduce the coefficient of friction between inorganic particle and reduce between organic matter
Cohesive force.Applicants have discovered that improving the toughness of chalk when the lubricant is paraffin and 1,2-PD.It is possible
The reason is that: contain rigid radical and long-chain, rigid radical and rigid radical, rigid base in the auxiliary agent and hydroxy phenyl silicone oil
Will form different aperture between group and long-chain and long-chain and long-chain, the small-molecule substance in lubricant is embedded between hole,
Reduce the movement between segment, while forming bridge between rigid radical, forms more perfect three around titanium dioxide
Structure is tieed up, the toughness of chalk is improved.
Preferably, the weight part ratio of paraffin and 1,2-PD is (4~8) in the lubricant: 1.
It is highly preferred that the weight part ratio of paraffin and 1,2-PD is 6:1 in the lubricant.
The paraffin is the hydrocarbon mixture that carbon atom number is about 18~30, and main component is linear paraffin (about 80%
~95%), there are also the monocyclic naphthenes of alkane and belt length side chain on a small quantity with individual branches (the two adds up to 20% or less content).
The paraffin is to freeze knot from the resulting lube cut of crude distillation through solvent refining, solvent dewaxing or through wax
Brilliant, squeezing, which dewaxes, is made slack wax, then through de-oiling, and sheet made from post-refining or acicular crystal.
In the application, the paraffin is selected from least one of microwax, atoleine, polyethylene wax.
The microwax is the mineral matter wax that a kind of molecular weight is high, fusing point is high, branched paraffin with higher, cyclic annular alkane
Hydrocarbon.The toughness of microwax is preferable in the application, has lower permeability to water vapour.It is colourless solid to white chunks under room temperature
Body, odorless tasteless, fusing point is 60~85 DEG C.
The atoleine refers to using kerosene or diesel oil distillate as raw material, through molecular sieve adsorbing separation or isopropanol-urea
Dewaxing, the obtained paraffin containing n-alkane；The atoleine either synthesized in coal/gas deliquescence process.
The polyethylene wax refers to the low molecular weight of the low molecular weight polyethylene that molecular weight is 1500-25000 or partial oxidation
Polyethylene.It is in granular form, white powder, bulk and milky are wax-like.With excellent mobility, electrical property, release property.
In a preferred embodiment, the paraffin is polyethylene wax.
The polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
As a preferred embodiment, the weight part ratio of the auxiliary agent, silicone oil, lubricant is (5~10): 1:(1~
3)。
As a preferred embodiment, the weight part ratio of the auxiliary agent, silicone oil, lubricant is (5~10): 1:2.
Preferably, the auxiliary agent, silicone oil, lubricant weight part ratio be 9:1:2.
In the application, the auxiliary agent, silicone oil and lubricant collective effect form more perfect three around titanium dioxide
Structure is tieed up, makes chalk that there is moderate hardness, weatherability and toughness.No matter one of three component is excessive or very few, all
The compactness and form that network structure can be destroyed, lead to the degradation of chalk.
The second aspect of the present invention provides the preparation method of the dust-free chalk, at least includes the following steps:
S1 sequentially adds white oil, lubricant in stirring container, at 70~100 DEG C of temperature, stirs evenly；
S2 sequentially adds titanium dioxide, auxiliary agent, silicone oil in the stirring container of step S1, and at 80~100 DEG C of temperature, stirring is equal
It is even；
S3 by step S2 mixture injection mold, compacting, cooling, be cut into finished product, packaging, to obtain the final product.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment
Embodiment 1
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 60 parts of titanium dioxide, auxiliary agent 10
Part, 3 parts of white oil, 1 part of silicone oil, 3 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 70% monoglyceride and 30% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive Decyl Polyglucoside；
The preparation method of the positive decyl glucosides, comprising the following steps:
(1) 6mol Decanol, 1mol glucose are added and have reflux condensate device, thermometer, blender and vacuum system
In the four-hole boiling flask of system, heat to 110 DEG C, it is to be mixed uniformly after, a certain amount of p-methyl benzenesulfonic acid is added, controls pressure
3kPa~4kPa；
(2) after reacting 4h, solution temperature is down to 60 DEG C, under normal pressure, 5% sodium hydroxide solution is added, by solution
PH=8 is neutralized, oligomerization sugar, vacuum distillation, except excessive alcohol in dereaction, then using solvent by remnants' are removed by filtration
Alcohol extraction and separation come out to get.
The weight of p-methyl benzenesulfonic acid is the 1% of the sum of Decanol and grape sugar weight in step (1).
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil.
The preparation method of the hydroxy phenyl silicone oil, comprising the following steps:
(1) under nitrogen protection atmosphere, 0.04mol diphenyl silanediol, 0.08mol pyridine and 20gTHF are mixed in
40 DEG C are warming up in 250mL single port bottle and by temperature；
(2) by dimethyldichlorosilane, the mixture of 20.0g THF composition is added dropwise in the mixture of step (1), drips
Add into rear the reaction was continued 6h.
(3) reaction mixture is after the post-processings such as decompression, centrifugation and decompression remove most of low-boiling compound,
The hydroxy phenyl silicone oil that pyridine salt solvent and by-product are 1% to get hydroxyl mass fraction.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, comprising the following steps:
S1 sequentially adds white oil, lubricant in stirring container, at 80 DEG C of temperature, stirs evenly；
S2 sequentially adds titanium dioxide, auxiliary agent, silicone oil in the stirring container of step S1, at 85 DEG C of temperature, stirs evenly；
S3 by step S2 mixture injection mold, compacting, cooling, be cut into finished product, packaging, to obtain the final product.
Embodiment 2
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 90 parts of titanium dioxide, auxiliary agent 50
Part, 15 parts of white oil, 10 parts of silicone oil, 15 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 70% monoglyceride and 30% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive Decyl Polyglucoside；
The preparation method is the same as that of Example 1 for the positive decyl glucosides.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 3
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 70% monoglyceride and 30% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive Decyl Polyglucoside；
The preparation method is the same as that of Example 1 for the positive decyl glucosides.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 4
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 90% monoglyceride and 10% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive Decyl Polyglucoside；
The preparation method is the same as that of Example 1 for the positive decyl glucosides.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 5
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive Decyl Polyglucoside；
The preparation method is the same as that of Example 1 for the positive decyl glucosides.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 6
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are n-dodecyl polyglucoside；
The preparation method is the same as that of Example 1 for the n-dodecyl polyglucoside, the difference lies in that the alcohol is n-dodecanol.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 7
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive undecyl glucosides；
The preparation method is the same as that of Example 1 for the n-undecane base glucosides, the tip-nip the difference lies in that alcohol is positive.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 1% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 8
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive undecyl glucosides；
The preparation method is the same as that of Example 1 for the n-undecane base glucosides, the tip-nip the difference lies in that alcohol is positive.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 10% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for base phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 9
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive undecyl glucosides；
The preparation method is the same as that of Example 1 for the n-undecane base glucosides, the tip-nip the difference lies in that alcohol is positive.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 3% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 4:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 10
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive undecyl glucosides；
The preparation method is the same as that of Example 1 for the n-undecane base glucosides, the tip-nip the difference lies in that alcohol is positive.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 3% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 8:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 11
A kind of high rigidity antiskid nanometer dust-free chalk, by weight, including following components: 75 parts of titanium dioxide, auxiliary agent 35
Part, 10 parts of white oil, 5 parts of silicone oil, 10 parts of lubricant；
The titanium dioxide is rutile type titanium white, is bought in Hebei Bo Feng Chemical Co., Ltd., model BR648.
The auxiliary agent is that 80% monoglyceride and 20% alkyl glycosides form by weight percent, and the monoglyceride is hard
Glycerol, the alkyl glycosides are positive undecyl glucosides；
The preparation method is the same as that of Example 1 for the n-undecane base glucosides, the tip-nip the difference lies in that alcohol is positive.
White oil (model: the 10#) purchase is in Wuxi City Xin Su grease Co., Ltd.
The silicone oil is hydroxy phenyl silicone oil, and the mass fraction of hydroxyl is 3% in the hydroxy phenyl silicone oil, the hydroxyl
The preparation method is the same as that of Example 1 for phenyl silicone oil.
The lubricant is paraffin and 1,2-PD, and the weight part ratio of the paraffin and 1,2-PD is 6:1, described
Paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 12
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 11, the difference lies in that described
45 parts of auxiliary agent；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 13
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Auxiliary agent is undecyl glucosides；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 14
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Auxiliary agent is tristerin；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 15
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Alkyl glycosides is positive myristyl glucosides；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 16
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Alkyl glycosides is n-heptyl glucosides；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 17
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Silicone oil is phenyl silicone oil；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 18
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Lubricant is paraffin, and the paraffin is polyethylene wax, and the polyethylene wax (model: A-C6A) buys Yu Kaiyin chemical industry.
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 19
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Lubricant is 1,2- propylene glycol；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Embodiment 20
A kind of high rigidity antiskid nanometer dust-free chalk, concrete component and parts by weight are with embodiment 12, the difference lies in that described
Auxiliary agent is 10 parts；
The preparation method of the dust-free chalk, the specific steps are the same as those in embodiment 1.
Performance test
The dust-free chalk described in embodiment is tested for the property.
Fold resistance test: fixing in the position apart from the 1cm of both ends at, then in chalk length midpoint with without stretching
The cotton rope of contracting vacantly hangs polybag, and it is 30mm nail that length is then added into sack, until chalk fractures, then to adding
The nail added is counted.10 chalks are tested altogether, then averaging.Unit: root.
Dust generates measurement: high together with the blackboard bottom lateral distance about 2cm of 2.5mm length and with blackboard bottom
The deep paper groove of position setting 5cm wide, 3cm, blackboard is divided into the grid of 4cm X 4cm, then writes ancient poetry " quiet night thinks "
Five times, font size expires lattice as far as possible, and test is completed by the same person, and often tests a chalk and rest 10 minutes, collects
Dust and weighing in paper groove.10 chalks are tested altogether, then averaging.Unit: mg.
Dust-free chalk the performance test results described in 1. embodiment of table
The above described is only a preferred embodiment of the present invention, be not the limitation for making other forms to invention, it is any
Those skilled in the art are changed or are changed to the equivalent of equivalent variations possibly also with the technology contents of the disclosure above
Embodiment, but without departing from the technical solutions of the present invention, above embodiments are made according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of high rigidity antiskid nanometer dust-free chalk, which is characterized in that by weight, including following components: titanium dioxide 60-
90 parts, 10-50 parts of auxiliary agent；
Wherein, the auxiliary agent is made of monoglyceride and alkyl glycosides.
2. dust-free chalk as described in claim 1, which is characterized in that the list that the auxiliary agent is 70~90% by weight percent
Sweet ester and 10~30% alkyl glycosides composition.
3. dust-free chalk as claimed in claim 2, which is characterized in that the monoglyceride that the auxiliary agent is 80% by weight percent
Alkyl glycosides with 20% forms.
4. dust-free chalk as described in claim 1, which is characterized in that it is sweet that the monoglyceride is selected from olein, linoleic acid
Grease, tripalmitin, Compritol 888 ATO, tristerin, glyceryl laurate ester, in glyceryl linolenate at least
It is a kind of.
5. dust-free chalk as described in claim 1, which is characterized in that by weight, the dust-free chalk further includes white oil
3-15 parts, 1~10 part of silicone oil, 3~15 parts of lubricant.
6. dust-free chalk as claimed in claim 5, which is characterized in that the lubricant is selected from paraffin, calcium stearate, stearic acid
At least one of pentaerythritol ester, adipic acid pentaerythritol ester, 1,2- propylene glycol, zinc stearate, glycerol.
7. dust-free chalk as claimed in claim 6, which is characterized in that the lubricant is paraffin and/or 1,2-PD.
8. dust-free chalk as claimed in claim 5, which is characterized in that the auxiliary agent, silicone oil, lubricant weight part ratio be (5
~10): 1:(1~3).
9. dust-free chalk as claimed in claim 8, which is characterized in that the auxiliary agent, silicone oil, lubricant weight part ratio be (5
~10): 1:2.
10. according to the preparation method of the described in any item dust-free chalks of claim 5~9, which is characterized in that include at least following
Step:
S1 sequentially adds white oil, lubricant in stirring container, at 70~100 DEG C of temperature, stirs evenly；
S2 sequentially adds titanium dioxide, auxiliary agent, silicone oil in the stirring container of step S1, at 80~100 DEG C of temperature, stirs evenly；
S3 by step S2 mixture injection mold, compacting, cooling, be cut into finished product, packaging, to obtain the final product.
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Citations (4)
| 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 |
| KR20100022946A (en) * | 2009-09-24 | 2010-03-03 | 주식회사 유니바이오 | The composition and method to manufacture pastel crayon for diy(do it yourself) |
| 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 |
-
2019
- 2019-02-25 CN CN201910138660.9A patent/CN110003720B/en active Active
Patent Citations (4)
| 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 |
| KR20100022946A (en) * | 2009-09-24 | 2010-03-03 | 주식회사 유니바이오 | The composition and method to manufacture pastel crayon for diy(do it yourself) |
| 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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