CN111019398A - Surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate - Google Patents

Surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate Download PDF

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CN111019398A
CN111019398A CN201911329691.9A CN201911329691A CN111019398A CN 111019398 A CN111019398 A CN 111019398A CN 201911329691 A CN201911329691 A CN 201911329691A CN 111019398 A CN111019398 A CN 111019398A
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calcium carbonate
treatment method
surface treatment
hydrophobic properties
improving
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唐文
易双
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Hezhou Zhongshan Suawin Calcium Carbonate New Material Co ltd
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Hezhou Zhongshan Suawin Calcium Carbonate New Material Co ltd
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate, which comprises the following steps: s1, selecting limestone transported from a material field, cleaning, removing impurities, airing stone materials to remove surface moisture, and crushing the stone materials by a crusher to obtain calcium carbonate crushed materials; s2, conveying the crushed calcium carbonate obtained in the step S1 into a vertical mill, and synchronously adding a grinding aid and grinding to obtain calcium carbonate fine powder; s3, grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare calcium carbonate powder; s4, adding a modifier into the calcium carbonate powder prepared in the step S3, and then stirring to prepare a mixture; s5: and (4) drying, grinding and sieving the mixture prepared in the step S4 to prepare the modified calcium carbonate. The surface treatment method is simple, the production efficiency is high, and the oleophylic and hydrophobic properties of the calcium carbonate can be improved.

Description

Surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of calcium carbonate modification, and particularly relates to a surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate.
[ background of the invention ]
Calcium carbonate is a common inorganic filler, and is widely used in the fields of plastics and the like due to wide sources, low price and the like. However, unmodified calcium carbonate has the problems of surface hydrophilicity and lipophobicity, high specific surface energy, easy agglomeration among particles and the like, and has poor compatibility with plastics. Therefore, when the calcium carbonate is filled into plastics, the surface of the calcium carbonate must be modified to ensure that the surface of the calcium carbonate is oleophilic and hydrophobic, the compatibility with the plastics is enhanced, the dispersibility in the plastics is improved, and the mechanical property of the plastics is improved, so that the high-performance plastics are prepared.
[ summary of the invention ]
The invention provides a surface treatment method for improving the oleophylic and hydrophobic properties of calcium carbonate, which aims to solve the problem of poor oleophylic and hydrophobic properties of the surface of calcium carbonate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate comprises the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, synchronously adding a grinding aid, and grinding to prepare calcium carbonate fine stone powder;
s3: grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare calcium carbonate powder;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 2.3-3% of the weight of the calcium carbonate powder, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 8-13:5-9:1-2:2-3, and stirring at the speed of 2000-3000r/min to prepare a mixture;
s5: and (5) drying the mixture prepared in the step (S4) until the water content is less than or equal to 0.6%, grinding and sieving to obtain the modified calcium carbonate.
Preferably, the grinding aid in step S2 consists of sodium lignosulfonate, triisopropanolamine.
Preferably, the weight ratio of the sodium lignin sulfonate to the triisopropanolamine is 1: 3.5-6.
Preferably, the grinding aid is added in step S2 in an amount of 2.6 to 3.2% by weight of the crushed weight of calcium carbonate.
Preferably, the mesh number of the calcium carbonate powder in the step S3 is 100-200 meshes.
Preferably, the stirring time in step S4 is 60-90 min.
Preferably, the temperature for drying in step S5 is 46-50 ℃.
The invention has the following beneficial effects:
(1) during the grinding process of calcium carbonate, sodium lignosulfonate can destroy the crystal structure and absorb electrostatic charges to prevent the agglomeration of dispersed particles of calcium carbonate powder; triisopropanolamine has good dispersion effect, and is beneficial to the dispersion of ground calcium carbonate powder; the sodium lignosulfonate and the triisopropanolamine are compounded for use, so that the grinding efficiency of the calcium carbonate can be improved, the dispersibility of the calcium carbonate powder is changed, the electrostatic adsorption of calcium carbonate fine particles is effectively eliminated, the dispersed particles of the calcium carbonate powder are prevented from agglomerating, and good conditions are provided for subsequent modification.
(2) In the modifier, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is not within the range of the ratio of 8-13:5-9:1-2:2-3, so that the impact strength of the plastic is greatly reduced, and therefore, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate needs to be strictly controlled in actual production, so that the impact strength of the plastic is not influenced.
(3) The surface treatment method is simple, the production efficiency is high, and the oleophylic and hydrophobic properties of the calcium carbonate can be improved.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the preparation method of the modified calcium carbonate for high-performance plastics comprises the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, and synchronously adding a grinding aid consisting of sodium lignosulfonate and triisopropanolamine, and grinding, wherein the addition amount of the grinding aid is 2.6-3.2% of the crushed weight of the calcium carbonate, and the weight ratio of the sodium lignosulfonate to the triisopropanolamine is 1:3.5-6, so as to prepare calcium carbonate fine powder;
s3: classifying the calcium carbonate fine powder prepared in the step S2 by using a classifier to prepare 100-200-mesh calcium carbonate powder;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 2.3-3% of the weight of the calcium carbonate powder, the weight ratio of the α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 8-13:5-9:1-2:2-3, and stirring is carried out at the speed of 3000r/min of 2000-3000r/min for 60-90min to prepare a mixture;
s5: drying the mixture prepared in the step S4 at the temperature of 46-50 ℃ until the water content is less than or equal to 0.6%, grinding and sieving to prepare 1000-sand 1200-mesh modified calcium carbonate.
The application of the modified calcium carbonate in high-performance plastics comprises the following raw materials in percentage by mass: 48.3-53.9% of polyvinyl chloride, 38-42% of modified calcium carbonate, 3.2-4.6% of chlorinated paraffin, 0.8-1.1% of heat stabilizer, 1.8-2.1% of plasticizer and 2-2.3% of toughening agent;
the heat stabilizer is a KSR organic rare earth composite stabilizer;
the plasticizer is dioctyl phthalate;
the toughening agent is a styrene-butadiene thermoplastic elastomer.
The preparation method of the high-performance plastic comprises the following steps:
s1, weighing the raw materials according to the formula, adding the raw materials into a high-speed stirrer, heating to 107 ℃ at 100-;
and S2, conveying the uniformly mixed material prepared in the step S1 to a double-screw extruder, and performing melt blending extrusion granulation to prepare the high-performance plastic.
The present invention is illustrated by the following more specific examples.
Example 1
A preparation method of modified calcium carbonate for high-performance plastics comprises the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, and synchronously adding a grinding aid consisting of sodium lignosulfonate and triisopropanolamine, and grinding, wherein the addition amount of the grinding aid is 3% of the crushing weight of the calcium carbonate, and the weight ratio of the sodium lignosulfonate to the triisopropanolamine is 1:5.6, so as to prepare calcium carbonate fine powder;
s3: grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare calcium carbonate powder of 200 meshes;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 2.8% of the weight of the calcium carbonate powder, the weight ratio of the α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 12:7:1.4:2.9, and stirring at the speed of 3000r/min for 62min to prepare a mixture;
s5: and (4) drying the mixture prepared in the step S4 at the temperature of 48 ℃ until the water content is 0.5%, grinding and sieving to prepare the modified calcium carbonate of 1200 meshes.
The application of the modified calcium carbonate in high-performance plastics comprises the following raw materials in percentage by mass: 50.3% of polyvinyl chloride, 40% of modified calcium carbonate, 4.6% of chlorinated paraffin, 1% of heat stabilizer, 2.1% of plasticizer and 2% of toughening agent;
the heat stabilizer is a KSR organic rare earth composite stabilizer;
the plasticizer is dioctyl phthalate;
the toughening agent is a styrene-butadiene thermoplastic elastomer.
The preparation method of the high-performance plastic comprises the following steps:
(1) weighing the raw materials according to the formula, adding the raw materials into a high-speed stirrer, heating to 105 ℃, and uniformly stirring and mixing at the speed of 1500r/min to obtain a uniformly mixed material;
(2) and (2) conveying the uniformly mixed material prepared in the step (1) to a double-screw extruder, and performing melt blending extrusion granulation to obtain the high-performance plastic. The twin-screw extruder is divided into 9 sections, the set temperature is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃ and 240 ℃, the rotation speed of the main machine screw is 200r/min, and the head temperature is 240 ℃.
Example 2
A preparation method of modified calcium carbonate for high-performance plastics comprises the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, and synchronously adding a grinding aid consisting of sodium lignosulfonate and triisopropanolamine, and grinding, wherein the addition amount of the grinding aid is 2.7% of the crushed weight of the calcium carbonate, and the weight ratio of the sodium lignosulfonate to the triisopropanolamine is 1:3.8, so as to prepare calcium carbonate fine powder;
s3: grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare 100-mesh calcium carbonate powder;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 2.3% of the weight of the calcium carbonate powder, the weight ratio of the α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate to polysiloxane urethane acrylate is 8:6:1:3, and stirring for 86min at the speed of 2000r/min to prepare a mixture;
s5: and (4) drying the mixture prepared in the step S4 at the temperature of 46 ℃ until the water content is 0.6%, grinding the mixture to 1000 meshes, and sieving the ground product to obtain the modified calcium carbonate.
The application of the modified calcium carbonate in high-performance plastics comprises the following raw materials in percentage by mass: 53.9% of polyvinyl chloride, 38% of modified calcium carbonate, 3.2% of chlorinated paraffin, 0.8% of heat stabilizer, 1.8% of plasticizer and 2.3% of toughening agent;
the heat stabilizer is a KSR organic rare earth composite stabilizer;
the plasticizer is dioctyl phthalate;
the toughening agent is a styrene-butadiene thermoplastic elastomer.
The preparation method of the high-performance plastic comprises the following steps:
(1) weighing the raw materials according to the formula, adding the raw materials into a high-speed stirrer, heating to 102 ℃, and uniformly stirring and mixing at the speed of 1000r/min to obtain a uniformly mixed material;
(2) and (2) conveying the uniformly mixed material prepared in the step (1) to a double-screw extruder, and performing melt blending extrusion granulation to obtain the high-performance plastic. The twin-screw extruder is divided into 9 sections, the set temperature is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃ and 240 ℃, the rotation speed of the main machine screw is 200r/min, and the head temperature is 240 ℃.
Example 3
A preparation method of modified calcium carbonate for high-performance plastics comprises the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, and synchronously adding a grinding aid consisting of sodium lignosulfonate and triisopropanolamine, and grinding, wherein the addition amount of the grinding aid is 3.2% of the crushed weight of the calcium carbonate, and the weight ratio of the sodium lignosulfonate to the triisopropanolamine is 1:5.8, so as to prepare calcium carbonate fine powder;
s3: grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare calcium carbonate powder of 200 meshes;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 3% of the weight of the calcium carbonate powder, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate to polysiloxane urethane acrylate is 11:8:2:2.6, and stirring for 78min at the speed of 2500r/min to prepare a mixture;
s5: and (4) drying the mixture prepared in the step S4 at the temperature of 50 ℃ until the water content is 0.5%, grinding the mixture to 1000 meshes, and sieving the ground product to obtain the modified calcium carbonate.
The application of the modified calcium carbonate in high-performance plastics comprises the following raw materials in percentage by mass: 48.3% of polyvinyl chloride, 42% of modified calcium carbonate, 4.5% of chlorinated paraffin, 1.1% of heat stabilizer, 2% of plasticizer and 2.1% of toughening agent;
the heat stabilizer is a KSR organic rare earth composite stabilizer;
the plasticizer is dioctyl phthalate;
the toughening agent is a styrene-butadiene thermoplastic elastomer.
The preparation method of the high-performance plastic comprises the following steps:
(1) weighing the raw materials according to the formula, adding the raw materials into a high-speed stirrer, heating to 106 ℃, and uniformly stirring and mixing at the speed of 1200/min to obtain a uniformly mixed material;
(2) and (2) conveying the uniformly mixed material prepared in the step (1) to a double-screw extruder, and performing melt blending extrusion granulation to obtain the high-performance plastic. The twin-screw extruder is divided into 9 sections, the set temperature is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃ and 240 ℃, the rotation speed of the main machine screw is 200r/min, and the head temperature is 240 ℃.
Comparative example 1
The process for preparing modified calcium carbonate for high-performance plastics was substantially the same as that of example 1, except that no modifier was added in step S4.
Comparative example 2
The modified calcium carbonate for high performance plastics was prepared by the same procedure as in example 1 except that the modifier source material in step S4 lacked α -isotridecyl- ω -hydroxy-poly (oxy-1, 2-ethylene).
Comparative example 3
The preparation process of the modified calcium carbonate for high-performance plastics is basically the same as that of example 1, except that the raw material of the modifier in step S4 lacks fatty alcohol-polyoxyethylene ether ammonium sulfate.
Comparative example 4
The modified calcium carbonate for high-performance plastics was prepared by the same procedure as in example 1 except that the modifier material in step S4 lacks oleic acid diethanolamide borate ester.
Comparative example 5
The modified calcium carbonate for high-performance plastics was prepared by the same procedure as in example 1 except that the raw material of the modifier in step S4 lacks the silicone urethane acrylate.
Comparative example 6
The preparation process of the modified calcium carbonate for high-performance plastics is basically the same as that of example 1, except that the raw material proportion of the modifier in step S4 is different, namely, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 5:3:2: 3.
Comparative example 7
The preparation process of the modified calcium carbonate for high-performance plastics is basically the same as that of example 1, except that the raw material proportion of the modifier in step S4 is different, namely, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 17:13:1: 2.
Comparative example 8
The preparation process of the modified calcium carbonate for high-performance plastics is basically the same as that of example 1, except that the raw material proportion of the modifier in step S4 is different, namely, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 9:12:5: 2.
(I) Performance testing
The impact strengths of the plastics prepared in examples 1 to 3 and the plastics prepared in comparative examples 1 to 8 (plastics prepared by the plastic preparation process of example 1 using the modified calcium carbonates prepared in comparative examples 1 to 8) were measured, and the results are shown in Table 1 below.
The following criteria were used for testing:
GB/T1043-93 impact test method for plastic simply supported beam.
TABLE 1
Experimental project Impact Strength (kJ/m)2)
Example 1 48.91
Example 2 44.64
Example 3 47.12
Comparative example 1 16.84
Comparative example 2 43.16
Comparative example 3 39.71
Comparative example 4 41.58
Comparative example 5 42.63
Comparative example 6 40.78
Comparative example 7 38.96
Comparative example 8 42.57
It can be seen from table 1 that the absence of α -isotridecyl- ω -hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanolamide borate, silicone urethane acrylate, all greatly affect the modification of calcium carbonate from the data of example 1 and comparative examples 1-5, the absence of α -isotridecyl- ω -hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanolamide borate, silicone urethane acrylate, respectively, results in a decrease in impact strength of 13.32%, 23.17%, 2%, 14.73%, respectively, and the addition of α -isotridecyl- ω -hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol polyoxyethylene ether ammonium sulfate, oleic acid diethanolamide borate, silicone urethane acrylate, respectively, results in a synergistic increase in impact strength from the surfactant-urethane acrylate, silicone urethane acrylate, silicone urethane acrylate, silicone urethane acrylate, silicone urethane acrylate, silicone urethane acrylate, silicone acrylate.
Second, the influence of different modified calcium carbonate addition amounts on the impact properties of plastics is researched
The preparation process of the high-performance plastic is basically the same as that of example 1, except that experiments are carried out according to the addition amount of the modified calcium carbonate shown in Table 2, and the influence of different addition amounts of the modified calcium carbonate on the impact performance of the plastic is researched, and the results are shown in Table 2.
TABLE 2
Modified calcium carbonate addition amount/%) Impact Strength (kJ/m)2)
36 34.91
38 44.64
40 48.91
42 47.12
44 40.36
46 31.59
According to the experimental data in table 2, when the addition amount of the modified calcium carbonate is small, the probability of extrusion deformation between the particle groups existing in the plastic in an agglomerated form is small, so that the modified calcium carbonate cannot play a toughening role in the plastic; when the addition amount of the modified calcium carbonate is gradually increased, the probability of extrusion deformation of each particle group of the modified calcium carbonate is gradually increased, the modified calcium carbonate is gradually dispersed, and the impact energy can be effectively absorbed when the plastic is impacted, so that the impact strength of the plastic is improved; when the addition amount of the modified calcium carbonate is larger, the saturation of the pressure which can be borne by the plastic is exceeded, redundant modified calcium carbonate particles are accumulated into particle clusters with larger sizes, the plastic can be split when the plastic is impacted, and the impact strength of the plastic is further greatly reduced. It is also clear from the data in the table that the maximum impact strength of the plastics is 48.91kJ/m when the amount of modified calcium carbonate added is 40% by mass of the total raw materials for producing the plastics2Thus, it can be seen thatThe amount is the optimum addition amount.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate is characterized by comprising the following steps:
s1: cleaning limestone transported from a material field, removing impurities, airing stone to remove surface moisture, and crushing the stone by using a crusher to prepare a calcium carbonate crushed material;
s2: conveying the calcium carbonate crushed material prepared in the step S1 into a vertical mill, synchronously adding a grinding aid, and grinding to prepare calcium carbonate fine stone powder;
s3: grading the calcium carbonate fine powder prepared in the step S2 by using a grader to prepare calcium carbonate powder;
s4, adding a modifier into the calcium carbonate powder prepared in the step S3, wherein the modifier consists of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate, the addition amount of the modifier is 2.3-3% of the weight of the calcium carbonate powder, the weight ratio of α -isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), fatty alcohol-polyoxyethylene ether ammonium sulfate, oleic acid diethanol amide borate and polysiloxane urethane acrylate is 8-13:5-9:1-2:2-3, and stirring at the speed of 2000-3000r/min to prepare a mixture;
s5: and (5) drying the mixture prepared in the step (S4) until the water content is less than or equal to 0.6%, grinding and sieving to obtain the modified calcium carbonate.
2. The surface treatment method for improving the oleophilic and hydrophobic properties of calcium carbonate according to claim 1, wherein the grinding aid in step S2 consists of sodium lignosulfonate and triisopropanolamine.
3. The surface treatment method for improving the oleophilic and hydrophobic properties of calcium carbonate according to claim 2, wherein the weight ratio of the sodium lignosulfonate to the triisopropanolamine is 1: 3.5-6.
4. The surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate according to claim 1, wherein the grinding aid is added in an amount of 2.6-3.2% of the crushing weight of calcium carbonate in step S2.
5. The surface treatment method for improving oleophilic and hydrophobic properties of calcium carbonate as claimed in claim 1, wherein the mesh size of the calcium carbonate powder in step S3 is 100-200 mesh.
6. The surface treatment method for improving the oleophilic and hydrophobic properties of calcium carbonate according to claim 1, wherein the stirring time in step S4 is 60-90 min.
7. The surface treatment method for improving the oleophilic and hydrophobic properties of calcium carbonate according to claim 1, wherein the drying temperature in step S5 is 46-50 ℃.
CN201911329691.9A 2019-12-20 2019-12-20 Surface treatment method for improving oleophylic and hydrophobic properties of calcium carbonate Pending CN111019398A (en)

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* Cited by examiner, † Cited by third party
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CN108794932A (en) * 2018-06-29 2018-11-13 钦州市宝业坭兴陶厂 It a kind of method of modifying of nano-calcium carbonate and its applies in PVC wood plastic plank
CN108892886A (en) * 2018-05-24 2018-11-27 贺州钟山县双文碳酸钙新材料有限公司 Modified calcium carbonate Reinforced PVC tubing and preparation method
CN109181365A (en) * 2018-09-28 2019-01-11 贺州钟山县双文碳酸钙新材料有限公司 The processing method of high performance paints modified calcium carbonate

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CN108794932A (en) * 2018-06-29 2018-11-13 钦州市宝业坭兴陶厂 It a kind of method of modifying of nano-calcium carbonate and its applies in PVC wood plastic plank
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* Cited by examiner, † Cited by third party
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CN113522931A (en) * 2021-07-09 2021-10-22 浙江工业大学 Mineral oxidation acid production inhibition method based on in-situ rapid film formation on surface of sulfurized mineral

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Application publication date: 20200417