CN108410017A - A kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix - Google Patents

A kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix Download PDF

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CN108410017A
CN108410017A CN201810357664.1A CN201810357664A CN108410017A CN 108410017 A CN108410017 A CN 108410017A CN 201810357664 A CN201810357664 A CN 201810357664A CN 108410017 A CN108410017 A CN 108410017A
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barium sulfate
weight
composite material
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tio
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陈庆
司文彬
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Chengdu New Keli Chemical Science Co Ltd
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    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a kind of preparation methods for the high-dispersion barium sulfate composite material in plastic matrix, include the following steps：A, barium sulfate is impregnated with the titanium sulfate solution of low concentration；B, barium sulfate, dispersant and the urea liquid after dipping are mixed, the titanium sulfate solution of high concentration is added dropwise, reacted and nanometer BaSO is made4/TiO2Composite granule；C, composite granule, decontamination water and carboxy terminatedpolybutadiene ball milling are obtained into slurry；D, by slurry press filtration and drying, carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite material.The present invention utilizes the good dispersibility of nano-titanium dioxide and weatherability, BaSO obtained4/TiO2Composite granule granularity is smaller, particle diameter distribution is uniform, and has excellent uvioresistant ability, effectively improves dispersibility of the composite material in nonpolar solvent, composite material obtained has good dispersibility and brilliant looks form, for having good dispersion performance and processing performance in plastic matrix.

Description

A kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix
Technical field
The present invention relates to field of compound material, and in particular to for the filler in plastics, more particularly, to one kind for moulding Expect the preparation method of the high-dispersion barium sulfate composite material in masterbatch.
Background technology
Inorganic filler is with resourceful, cheap, description is varied, loading is big, toxicity is low, easy mixing The features such as processing, in recent years, in plastics, rubber, adhesive, papermaking, coating, chemical fibre, power electronics, ceramics, glass, fire proofed wood The application in the fields such as material, cementitious material, ink is more and more extensive.It is the most important field of inorganic filler that wherein plastics, which are industries,. By filler modified, plastics cost can be not only reduced, and its various performance can be significantly improved, assigns material new spy Sign expands it and quotes range.
In inorganic filler, barium sulfate is widely used in many industries such as rubber, plastics, ink, coating, papermaking.It receives Nano-barium sulfate has the important architectural characteristics such as quantum effect, dimensional effect, skin effect, and physical characteristic and common material are not Together, it is a kind of novel high-grade functional filling material, not only in many industrial circles such as rubber, plastics, ink, coating, papermaking It has broad application prospects, and broad prospect of application is had more in medicine, ceramics, composite material etc..In addition, dioxy It is a kind of best white inorganic pigment of current performance to change titanium, with anatase structures, Rutile structure and brookite modification Three kinds of crystal habits are present in nature, with nontoxic, best opacity, whiteness and brightness, stabilization physics and It is industrial to be widely used in coating, plastics, papermaking, printing, ink, chemical fibre and rubber etc. for chemical property.In recent years to barium sulfate It is increasingly taken seriously with the application of titanium dioxide in the plastic.
Number of patent application 201010596369.5 disclose a kind of polymolecularity blanc fixe for automobile plastic part and Preparation method.The preparation method includes the following steps：A, the barite progress of 95% or more barium content of selection is selected, cleans, dries in the air It is dry；B, the barite after drying carries out thunder mill after crushing on roller mill, its fineness is made to reach 400 mesh A derived above；C, to A Middle addition Sodium Polyacrylate dipersant, sericite in powder and allyl phenoxyacetate, are then ground with sand mill, mixture Particle diameter be less than or equal to 1.2 μm after dry, crush, obtain B；D, calcium carbonate, titanium dioxide and phenoxy acetic acid are added into B Allyl ester is adequately mixed to obtain product.Compared with prior art, the polymolecularity blanc fixe obtained of the invention has Following advantages：Fineness is small, good dispersion；It is of low cost；Small pollution of the environment in process of production.
Number of patent application 201410457100.7 disclose it is a kind of using barium carbonate synthesis barium sulfate production process in, simultaneously The production new technique of the inorganic agents such as aluminum sulfate and waterglass cladding barium sulfate particles is added.The technical process is as follows：By carbon Sour barium and the barium content 13-15% that dissociates in sulfuric acid reaction to slurries.Aluminum sulfate solution is added in cladding aluminum amount as required, is being added Sodium sulphate or sulfuric acid are to without the barium that dissociates.Waterglass is added in coated Si amount as required.It is adjusted by the way that sulfuric acid or sodium hydroxide is added Final acid-base value is to 8 ~ 9.Then it is filtered, washed, filter residue is the polymolecularity energy barium sulfate of silicon, aluminium inorganic coating.The invention Method reduction production cost, reduction wastewater discharge, the overall investment of reduction equipment, less energy consumption, simple for process and properties of product are excellent The features such as good stable.
Number of patent application 200910103012.6 discloses a kind of composite titanium dioxide, has kernel and coating layer, kernel It is less than 1 μm for granularity, barium sulfate and/or sulfuric acid strontium crystal of the whiteness more than 98%, coating layer is nm-class rutile-type dioxy Change titanium.The invention also discloses the preparation methods of the composite titanium dioxide, carry out as follows：（1）Barium sulfate or strontium sulfate Preparation；（2）Cladding processing；（3）Composite titanium dioxide high-temperature heat treatment；（4）Composite titanium dioxide post-processes.The invention passes through Chemical synthesis submicron spherical or subsphaeroidal barium sulfate or strontium sulfate, and by induced hydrolysis cladding titanium dioxide, make titanium dioxide Titanium homoepitaxial finally obtains the composite titanium dioxide granule-morphology of spherical or close quasi- ball-type, and granularity is small, size distribution model It encloses controllable.
Number of patent application 201410083355.1 discloses a kind of preparation method of high-dispersion barium sulfate, including walks as follows Suddenly：（1）Reaction process：Reactivity is added in 85% or more barium carbonate in metabisulfite solution, sulfuric acid is used in heating reaction The sodium carbonate that neutralization reaction system generates, it is 9.0 ~ 9.5 to maintain the pH value of reaction system；Sulfuric acid is gradually reduced later, and speed is added Degree, maintaining reaction solution system pH, the reaction was continued 7 or more, stops adding sulfuric acid later；（2）Purification process：In reaction solution Nitric acid is added, and maintains reaction solution pH in 4.0 ~ 4.5 ranges, is stirred to react, detaches；And（3）Finished product process：It will obtain Solid mashing, the barium sulfate product of high dispersive is obtained after alkali cleaning, separation, purification, drying.The invention additionally provides a kind of sulfuric acid Barium product purity is 99.40% or more, and Hegman fineness grind is at 7 microns or less；The organic system sedimentation time was at 4 hours or more；Whiteness is big In 99.0%, D50 between 1.30-1.50 microns.
It can be seen that barium sulfate or titanium dioxide for filling plastic when being modified in the prior art, generally existing powder The hydrophily of material surface is stronger, and the compatibility of especially barium sulfate and polymeric matrix is poor, bad dispersibility, directly application effect Fruit is bad, and granule-morphology indefinite form, it is wide that there are particle diameter distributions, and then the problems such as influence plastic matrix processing performance.
Invention content
Effectively to solve above-mentioned technical problem, the present invention proposes a kind of multiple for the high-dispersion barium sulfate in plastic matrix The preparation method of condensation material can effectively improve barium sulfate composite material dispersibility and brilliant looks form, have in plastic matrix Good dispersion performance and processing performance.
The specific technical solution of the present invention is as follows：
A kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix, the high-dispersion barium sulfate composite wood Material is to be complex as a nanometer BaSO by barium sulfate and generated in-situ titanium dioxide4/TiO2Composite granule, it is further poly- using carboxyl Butadiene carries out ball milling cladding and is made, and specific preparation process is：
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 20 ~ 30min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 10 ~ 15min in a heated condition, after the completion of reaction, filters, using deionized water Filter residue is washed, nanometer BaSO is made4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
Preferably, in the step a, the mass concentration of the titanium sulfate solution of low concentration is 20 ~ 30%.
Preferably, in the step b, the mass concentration of urea liquid is 35 ~ 50%, the matter of the titanium sulfate solution of high concentration Measure a concentration of 60 ~ 70%.
Preferably, in the step b, the parts by weight of each raw material are respectively, and 18 ~ 25 parts by weight of barium sulfate, urea liquid 33 ~ 51 parts by weight, 1 ~ 2 parts by weight of neopelex, 30 ~ 40 parts by weight of titanium sulfate solution of high concentration.
Preferably, in the step b, heating temperature is 140 ~ 170 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 5 ~ 8mL/min, reaction time are 4 ~ 6h.
Preferably, in the step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO235 ~ 50 weight of composite granule Measure part, 30 ~ 35 parts by weight of decontamination water, 20 ~ 30 parts by weight of carboxy terminatedpolybutadiene.
Preferably, in the step c, the circulating water pressure control of ball mill is 0.3 ~ 0.4MPa, compressed air pressure control It is made as 0.3 ~ 0.5MPa, ball mill inlet pressure is -2500 ~ -3000Pa, and outlet pressure is -4000 ~ -4500Pa.
Preferably, in the step d, it is 0.3 ~ 0.5MPa that press filtration, which uses plate and frame filter plate or chamber filter plate, operating pressure,.
Preferably, in the step d, the temperature of drying is 110 ~ 130 DEG C, and the time is 2 ~ 4h.
The defect that the barium sulfate usually prepared has granule-morphology indefinite form, particle diameter distribution wide, and nano-titanium dioxide has There are good dispersibility and weatherability, nanometer BaSO is prepared using hydro-thermal reaction method4/TiO2Composite granule, can be to the grain of powder Diameter and distribution are controlled, and grain size smaller, the powder of particle diameter distribution evenly is made.However, the agglomeration of small sized particles Obviously, when composite granule is directly added into polymeric matrix, it is difficult to be uniformly dispersed, polarity and nonpolar interface cohesion compared with Difference, hence it is evident that reduce the application effect to polymer.In the strand of carboxy terminatedpolybutadiene, butadiene segment is nonpolar section, carboxylic Base is highly polar group.Therefore, under the promotion of external force, the carboxyl of carboxy terminatedpolybutadiene can be combined with composite granule, be made compound The polar surfaces of powder are changed into apolar surfaces, and so as to well compatible with polymeric matrix, interface bond strength improves, and has Conducive to dispersed uniform.
The above of the present invention also proposed a kind of high-dispersion barium sulfate composite material in plastic matrix, mainly Using nano-titanium dioxide, shielding ultraviolet rays effect is strong, there is good dispersibility and a weatherability, the composite granule granularity of preparation compared with It is small, uniform, there is excellent uvioresistant ability, and uniformly coat one layer of carboxy terminatedpolybutadiene on it, so as to improve Dispersibility of the composite material in nonpolar solvent, dispersibility when improving for plastic matrix and processing performance.Main mistake Cheng Wei：A, barium sulfate is impregnated with the titanium sulfate solution of low concentration；B, by after dipping barium sulfate, dispersant and urea it is molten Liquid is mixed, and the titanium sulfate solution of high concentration is added dropwise, and reacts and nanometer BaSO is made4/TiO2Composite granule；It c, will be compound Powder, decontamination water and carboxy terminatedpolybutadiene ball milling obtain slurry；D, by slurry press filtration and drying.
Beneficial effects of the present invention are：
A kind of high dispersive in plastic matrix is prepared using carboxy terminatedpolybutadiene cladding barium sulfate/titanium dioxide 1. proposing The method of barium sulfate composite material.
2. the present invention is multiple using the good dispersibility of nano-titanium dioxide and weatherability, barium sulfate/titanium dioxide obtained Conjunction powder granularity is smaller, and particle diameter distribution is uniform, and has excellent uvioresistant ability.
3. the present invention uniformly coats one layer of carboxy terminatedpolybutadiene in preparing on barium sulfate/titanium dioxide composite powder, Dispersibility of the composite material in nonpolar solvent is effectively improved, composite material obtained has good dispersibility and brilliant looks Form, for having good dispersion performance and processing performance in plastic matrix.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 25min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 13min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 25%；In step b, the mass concentration of urea liquid It is 45%, the mass concentration of the titanium sulfate solution of high concentration is 65%；
In step b, heating temperature is 155 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 6mL/min, and the reaction time is 5h；In step c, the circulating water pressure control of ball mill is 0.3MPa, and compressed air pressure control is 0.4MPa, ball mill import Pressure is -2800Pa, and outlet pressure is -4300Pa；In step d, press filtration uses plate and frame filter plate, operating pressure 0.4MPa； It states in step d, the temperature of drying is 120 DEG C, time 3h；
In step b, the parts by weight of each raw material are respectively 22 parts by weight of barium sulfate, 42 parts by weight of urea liquid, detergent alkylate sulphur 1 parts by weight of sour sodium, 35 parts by weight of titanium sulfate solution of high concentration；In step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO242 parts by weight of composite granule, 33 parts by weight of decontamination water, 25 parts by weight of carboxy terminatedpolybutadiene.
Embodiment 2
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 22min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 11min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 22%；In step b, the mass concentration of urea liquid It is 36%, the mass concentration of the titanium sulfate solution of high concentration is 63%；
In step b, heating temperature is 150 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 6mL/min, and the reaction time is 5.5h；In step c, the control of the circulating water pressure of ball mill is 0.4MPa, and compressed air pressure control is 0.3MPa, ball mill into Mouth pressure is -2600Pa, and outlet pressure is -4300Pa；In step d, press filtration uses chamber filter plate, operating pressure 0.3MPa； It states in step d, the temperature of drying is 113 DEG C, time 3.5h；
In step b, the parts by weight of each raw material are respectively 19 parts by weight of barium sulfate, 48 parts by weight of urea liquid, detergent alkylate sulphur 2 parts by weight of sour sodium, 31 parts by weight of titanium sulfate solution of high concentration；In step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO247 parts by weight of composite granule, 31 parts by weight of decontamination water, 22 parts by weight of carboxy terminatedpolybutadiene.
Embodiment 3
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 28min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 14min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 27%；In step b, the mass concentration of urea liquid It is 45%, the mass concentration of the titanium sulfate solution of high concentration is 68%；
In step b, heating temperature is 160 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 7mL/min, and the reaction time is 5h；In step c, the circulating water pressure control of ball mill is 0.3MPa, and compressed air pressure control is 0.5MPa, ball mill import Pressure is -2900Pa, and outlet pressure is -4400Pa；In step d, press filtration uses plate and frame filter plate, operating pressure 0.5MPa； It states in step d, the temperature of drying is 125 DEG C, time 2.5h；
In step b, the parts by weight of each raw material are respectively 22 parts by weight of barium sulfate, 38 parts by weight of urea liquid, detergent alkylate sulphur 2 parts by weight of sour sodium, 38 parts by weight of titanium sulfate solution of high concentration；In step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO238 parts by weight of composite granule, 34 parts by weight of decontamination water, 28 parts by weight of carboxy terminatedpolybutadiene.
Embodiment 4
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 20min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 10min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 20%；In step b, the mass concentration of urea liquid It is 35%, the mass concentration of the titanium sulfate solution of high concentration is 60%；
In step b, heating temperature is 140 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 5mL/min, and the reaction time is 6h；In step c, the circulating water pressure control of ball mill is 0.3MPa, and compressed air pressure control is 0.3MPa, ball mill import Pressure is -2500Pa, and outlet pressure is -4000Pa；In step d, press filtration uses chamber filter plate, operating pressure 0.3MPa；It states In step d, the temperature of drying is 110 DEG C, time 4h；
In step b, the parts by weight of each raw material are respectively 18 parts by weight of barium sulfate, 51 parts by weight of urea liquid, detergent alkylate sulphur 1 parts by weight of sour sodium, 30 parts by weight of titanium sulfate solution of high concentration；In step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO250 parts by weight of composite granule, 30 parts by weight of decontamination water, 20 parts by weight of carboxy terminatedpolybutadiene.
Embodiment 5
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 30min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 15min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further Carboxy terminatedpolybutadiene is added, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 30%；In step b, the mass concentration of urea liquid It is 50%, the mass concentration of the titanium sulfate solution of high concentration is 70%；
In step b, heating temperature is 170 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 8mL/min, and the reaction time is 4h；In step c, the circulating water pressure control of ball mill is 0.4MPa, and compressed air pressure control is 0.5MPa, ball mill import Pressure is -3000Pa, and outlet pressure is -4500Pa；In step d, press filtration uses plate and frame filter plate, operating pressure 0.5MPa； It states in step d, the temperature of drying is 130 DEG C, time 2h；
In step b, the parts by weight of each raw material are respectively 25 parts by weight of barium sulfate, 33 parts by weight of urea liquid, detergent alkylate sulphur 2 parts by weight of sour sodium, 40 parts by weight of titanium sulfate solution of high concentration；In step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO235 parts by weight of composite granule, 35 parts by weight of decontamination water, 30 parts by weight of carboxy terminatedpolybutadiene.
Comparative example 1
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 25min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 13min in a heated condition, after the completion of reaction, filters, adopts and be washed with deionized Nanometer BaSO is made in filter residue4/TiO2Composite granule.
In step a, the mass concentration of the titanium sulfate solution of low concentration is 25%；In step b, the mass concentration of urea liquid It is 45%, the mass concentration of the titanium sulfate solution of high concentration is 65%；
In step b, heating temperature is 155 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 6mL/min, and the reaction time is 5h；
In step b, the parts by weight of each raw material are respectively 22 parts by weight of barium sulfate, 42 parts by weight of urea liquid, detergent alkylate sulphur 1 parts by weight of sour sodium, 35 parts by weight of titanium sulfate solution of high concentration.
BaSO made from above-described embodiment 1 ~ 5 and comparative example 14/TiO2Composite granule tests its granularity, particle diameter distribution, with And the dispersing character in igelite master batch obtained, method or the condition for testing characterization are as follows：
Composite material granularity and particle diameter distribution：Using wet dispersion technology, composite sample is taken, machinery in deionized water is added Stirring makes sample uniformly scatter；Then decentralized medium and sample are put into laser particle size analyzer, start ultrasonic generator Keep sample fully dispersed, then start circulating pump, tested, automatically generates particle size distribution data table, grading curve, i.e., The average grain diameter and Size Distribution of composite material can be obtained.
Dispersing character in masterbatch：Composite material is added according to mass fraction 40% in Corvic, extruding pelletization obtains To igelite master batch.Using dispersing character of the SEM scanning electron microscopic observation composite materials in masterbatch.
The results are shown in Table 1.
Table 1：

Claims (9)

1. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix, it is characterised in that：The high score It is to be complex as a nanometer BaSO by barium sulfate and generated in-situ titanium dioxide to dissipate barium sulfate composite material4/TiO2Composite granule, into One step carries out ball milling cladding using carboxy terminatedpolybutadiene and is made, and specific preparation process is：
A, it filters and takes out by barium sulfate impregnation in the titanium sulfate solution of low concentration, after 20 ~ 30min；
B, the barium sulfate after dipping is mixed with urea liquid, neopelex is added as dispersant, is dispersed with stirring The titanium sulfate solution of high concentration is added dropwise in 10 ~ 15min in a heated condition, after the completion of reaction, filters, using deionized water Filter residue is washed, nanometer BaSO is made4/TiO2Composite granule；
C, the nanometer BaSO for obtaining step b4/TiO2Composite granule stirs evenly in the ball mill with decontamination water, further adds Enter carboxy terminatedpolybutadiene, ball milling obtains slurry；
D, the slurry for obtaining step c carries out press filtration and drying, and carboxy terminatedpolybutadiene is made and coats BaSO4/TiO2Composite wood Material.
2. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step a, the mass concentration of the titanium sulfate solution of low concentration is 20 ~ 30%.
3. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step b, the mass concentration of urea liquid is 35 ~ 50%, the mass concentration of the titanium sulfate solution of high concentration It is 60 ~ 70%.
4. according to a kind of any one of claims 1 to 3 system for the high-dispersion barium sulfate composite material in plastic matrix Preparation Method, it is characterised in that：In the step b, the parts by weight of each raw material are respectively 18 ~ 25 parts by weight of barium sulfate, urea liquid 33 ~ 51 parts by weight, 1 ~ 2 parts by weight of neopelex, 30 ~ 40 parts by weight of titanium sulfate solution of high concentration.
5. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step b, heating temperature is 140 ~ 170 DEG C, and the rate of addition of the titanium sulfate solution of high concentration is 5 ~ 8mL/ Min, reaction time are 4 ~ 6h.
6. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step c, the parts by weight of each raw material are respectively nanometer BaSO4/TiO235 ~ 50 parts by weight of composite granule are gone 30 ~ 35 parts by weight of water impurity, 20 ~ 30 parts by weight of carboxy terminatedpolybutadiene.
7. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step c, the circulating water pressure control of ball mill is 0.3 ~ 0.4MPa, and compressed air pressure control is 0.3 ~ 0.5MPa, ball mill inlet pressure are -2500 ~ -3000Pa, and outlet pressure is -4000 ~ -4500Pa.
8. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step d, it is 0.3 ~ 0.5MPa that press filtration, which uses plate and frame filter plate or chamber filter plate, operating pressure,.
9. a kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix according to claim 1, It is characterized in that：In the step d, the temperature of drying is 110 ~ 130 DEG C, and the time is 2 ~ 4h.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110339864A (en) * 2019-07-25 2019-10-18 河南嘉利美环保材料有限公司 One kind containing TiO2The spheric granules of purification factor
CN111961304A (en) * 2020-08-21 2020-11-20 安徽江淮汽车集团股份有限公司 Polymethyl methacrylate composite material and preparation method thereof
CN113234255A (en) * 2021-05-07 2021-08-10 江苏群鑫粉体科技股份有限公司 Ultraviolet screening agent and preparation method and application thereof
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CN116179195A (en) * 2023-02-09 2023-05-30 佛山安亿纳米材料有限公司 Quantum dot composite material and preparation method and application thereof

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