CN107344990A - A kind of preparation method for the modified gypsum base whisker of activeness and quietness plastics and its based on emulsion polymerization - Google Patents
A kind of preparation method for the modified gypsum base whisker of activeness and quietness plastics and its based on emulsion polymerization Download PDFInfo
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- CN107344990A CN107344990A CN201610294668.0A CN201610294668A CN107344990A CN 107344990 A CN107344990 A CN 107344990A CN 201610294668 A CN201610294668 A CN 201610294668A CN 107344990 A CN107344990 A CN 107344990A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- 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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- 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
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- 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
Abstract
The invention discloses a kind of modified gypsum base whisker for activeness and quietness plastics, using core shell structure of the calcium sulfate crystal whiskers as kernel, elastomer for external coating, it can be used in the functional modification of plastics.The present invention pre-processes to calcium sulfate crystal whiskers first, efficiently solve the problems, such as dehydration disintegration of the whisker in high temperature extrusion, then by in-situ emulsion polymerization Process Production elastomer and in calcium sulfate crystal whiskers Surface coating, formed using hemihydrate calcium sulfate crystal whisker as core, elastomer is the core/shell structure of shell, use it for the modification of PVC hard materials, hence it is evident that play the good result of activeness and quietness.
Description
Technical field
The present invention relates to a kind of modified gypsum base whisker for activeness and quietness plastics and its preparation method based on emulsion polymerization, phosphorus
Chemical industry preparing technical field.
Background technology
Polyvinyl chloride (Polyvinyl chloride, abbreviation PVC) resin is by vinyl chloride (Vinyl Chloride, abbreviation
VC) the thermoplastic high molecular compound that monomer is polymerized.
It can be determined that PVC belongs to fragile material category by Vincent polymer fragility-ductile rupture theory, and
The fragility of PVC material seriously constrains its production and application, so the toughening modifying research to PVC material is commercial Application
Field urgent problem to be solved, and prepare the inevitable requirement of high-performance PVC (polyvinyl chloride) composite.Further, since polyvinyl chloride resin
In the presence of some defects, typically can not directly use it for producing, it is necessary to add the ability such as corresponding stabilizer, modifying agent and auxiliary agent
It is a large amount of to go into operation.Fluidity of molten is poor in process of production for hard PVC simultaneously, processing difficulties, and its product impact resistance, heat are steady
It is qualitative, weatherability is bad, if not being modified processing to hard PVC material, can only use it to produce low performance requirement
Section bar, tubing, application are narrow.On the basis of not to damage the strength of materials and other physical property, improve simultaneously
The toughness of PVC product, the engineer applied field for widening PVC is extremely important.
Glass fibre (abbreviation glass GF) is made in nineteen thirty-nine, the mankind for the first time, and glass initially enters engineer applied field.With
Fiberglass reinforced modified PVC, the bending strength, tensile strength and impact strength of PVC composites can be improved.In certain model
In enclosing, with the increase of glass fiber content, bending strength, tensile strength, impact strength increase therewith.Due to fiberglass reinforced
PVC has good mechanical property, thus can be widely used as structural material.But the processing of fiberglass reinforced PVC material
Difficulty is big, product poor heat resistance, and dispersiveness, uniformity are difficult to control, therefore glass fiber reinforced materials are difficult to turn into Plastics Processing Industry
Main material, it is impossible to carry out large-scale production and application, be especially restricted in the production field of large piece.
Haloflex (CPE) is a kind of macromolecular elastomer material, be by high density polyethylene (HDPE) (HDPE) through chlorination and
It is made.The Novel modifier CPE Tyrim2500p of Dow Chemical company research and development, can significantly improve hard PVC product
Low temperature impact properties.But just seeing at present, for domestic CPE than other functional stuffings, CPE modified effect is poor, into
This height, its erosion-resisting characteristics is poor, and can reduce PVC product intensity.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of activeness and quietness that is used for for above-mentioned the shortcomings of the prior art and mould
The modified gypsum base whisker of material and its preparation method based on emulsion polymerization, it is good with PVC rigid plastics compatibility, and to PVC
The mechanics and heat-proof quality of material carry out functional modification, effectively improve the intensity, toughness and dimensional stability of plastic material.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
A kind of modified gypsum base whisker for activeness and quietness plastics, it is external coating by kernel, elastomer of calcium sulfate crystal whiskers
Core shell structure, it can be used in the functional modification of plastics.
By such scheme, the plastics are PVC rigid plastics.
By such scheme, the elastomer is polybutyl methacrylate etc..
By such scheme, for the Calcium Sulfate Whiskers in 1-10 μ ms, draw ratio is no more than 10.The calcium sulfate crystal whiskers
Can be anhydrous calcium sulfate whisker, hemihydrate calcium sulfate crystal whisker, Dihydrate gypsum whiskers, hemihydrate calcium sulfate crystal whisker can be α-half water
Calcium sulfate crystal whiskers.
By such scheme, for the diameter of α-hemihydrate calcium sulfate crystal whisker in 1-10 μ ms, draw ratio is no more than 10, can use
It is prepared by following method：Compound concentration scope adds ardealite and crystalline substance in 20%-30% (mass fraction) heat stabilizer solution
Type adjusting control agent reacts 4-6 hours under the conditions of 80-95 DEG C of normal pressure, then filters while hot, filter cake is placed on into vacuum drying chamber does
It is dry, it is α-hemihydrate calcium sulfate crystal whisker after drying.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:
(4~8)；The addition of crystal polymorph control agent is the 0.05-0.15% of phosphogypsum quality.
Specifically, the ardealite is the ardealite after purification, can use solid slag ardealite as raw material, anti-through synthesizing
It, should filter, dissolve by heating, heat filtering and crystallisation by cooling obtain.
Specifically, the whisker heat stabilizer solution is the NaCl solution and K that mass fraction is 20%-30%2SO4Solution is pressed
1:(0.1-10) volume mixture is formulated；Or the whisker heat stabilizer solution is that mass fraction is 20%-30%'s
NaCl solution and CaCl2Solution presses 1:(0.1-10) volume mixture is formulated.
Specifically, the crystal polymorph control agent is multicomponent organic acid and/or multicomponent organic acid salt.Preferably, the crystal polymorph control agent is
The mixture of sodium citrate and sodium gluconate, sodium citrate and sodium gluconate quality proportioning scope control are 1：(0.1~10).
Above-mentioned preparation method of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics, comprise the following steps：
(1) calcium sulfate crystal whiskers are chosen, for diameter in 1-10 μ ms, draw ratio is no more than 10；By mass percentage,
Weigh elastomeric precursors 35-40%, calcium sulfate crystal whiskers 12-20%, dispersant 15-23%, emulsifying agent 18-25%, initiator 3-
5%；Dispersant, emulsifying agent, initiator, elastomeric precursors are divided into two batches；
(2) mass fraction 3%-5% KH-550 acetone solns are prepared, are discharged after calcium sulfate crystal whiskers are added thereto into mixing,
Modified calcium sulfate crystal whiskers are obtained after drying；
(3) elastomeric precursors and modified calcium sulfate crystal whiskers are mixed in water, and add part dispersant, emulsifying agent,
Heating water bath carries out graft polymerization reaction after initiator is well mixed, is demulsified, filters, dries after the completion of reaction, obtains calcium sulfate
The compound intermediate emulsion seed of whisker-elastomer；
(4) dispersant of surplus, emulsifying agent will be added in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-elastomer, drawn
Hair agent, elastomeric precursors and water carry out graft polymerization reaction again, generate calcium sulfate crystal whiskers/elastomer composite breast of core/shell structure
Liquid, then through demulsification, suction filtration and drying steps, the core shell structure particle of calcium sulfate crystal whiskers/elastomer is obtained, that is, is used to strengthen
The modified gypsum base whisker of toughened plastics.
By such scheme, one or more of the dispersant in isobutanol, polyvinyl alcohol.
By such scheme, one or more of the emulsifying agent in neopelex, dodecyl sodium sulfate.
By such scheme, the initiator is selected from redox system initiator, by mass percentage, oxidant and reducing agent
Mol ratio is (1~1.2)：1.
By such scheme, the elastomeric precursors are butyl methacrylate etc..
By such scheme, the dispersant, emulsifying agent, initiator and elastomeric precursors are divided into two batches, first batch and
Two batch dosage mass ratioes are 1：2~3.
By such scheme, in the step (1) by mass percentage, elastomeric precursors 37-39%, calcium sulfate crystal whiskers 15-
17%th, dispersant 17-19%, emulsifying agent 20-22%, initiator 3-5%.
By such scheme, mass fraction 3%-5% KH-550 acetone soln compound methods are in step (2)：By KH-550
It is dissolved in acetone, it is not necessary to add aqueous solvent, what 3-5% was said is the mass contents of KH-550 in acetone.
By such scheme, the graft polymerization reaction condition in the step (3) is：Under inert atmosphere, polymerization temperature control exists
70-80 DEG C, polymerization time was controlled in 4-6 hours.
By such scheme, the graft polymerization reaction condition in the step (4) is：Under inert atmosphere, polymerization temperature control exists
50-70 DEG C, polymerization reaction time was controlled in 4-6 hours.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present invention and PVC rigid plastics adds double screw extruder
Extruding pelletization is carried out, produces tough-increased and reinforced modification plastics.Specifically, during the extruding pelletization, screw speed be 120-300 turn/
Minute, temperature is 170-220 DEG C.
The present invention is set out with the calcium sulfate crystal whiskers of ideal dimensions, and hydrophobic place is carried out to the whisker with the acetone soln of silane coupler
Reason, efficiently solves the problems, such as dehydration disintegration of the whisker in high temperature extrusion, then adds elastomeric precursors, passes through breast in situ
Liquid polymerization technique makes it fully polymerize, and is coated on whisker surface, and the core/shell structure of the elastomer of cladding calcium sulfate crystal whiskers is made
(i.e. a kind of activeness and quietness modifying agent), as applying filler in PVC rigid plastics.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the present invention makees PVC reinforcer and infrared function of heat reflection filler using calcium sulfate crystal whiskers, and passes through emulsion polymerization technology
In whisker Surface coating elastomer, the core/shell structure with the good whisker-elastomer of PVC rigid plastics compatibility is formed, so it is right
The mechanics and heat-proof quality of PVC material carry out functional modification, and its process is green, and processing characteristics is good, and cost is low.
2nd, the present invention can be by being prepared into whisker by phosphorus ore association calcium resource, and raw material is phosphorous chemical industry solid waste, and cost is low；Gained
Calcium sulphate-based whisker heat decomposition temperature it is higher, efficiently solve what under the hot conditions in emulsion polymerization stage whisker dehydration was disintegrated
Problem；Whisker surface is through hydrophobic modified and elastomeric precursors polymerization cladding, the elastomer coated inorganic rigid particle structure pair of formation
Rigid plastics has excellent activeness and quietness effect.
3rd, the present invention, which combines, adds influence of the sodium ion to thermodynamic behavior in semi-hydrated gypsum whisker, utilize phosphorus ore association calcium resource
By adding crystal polymorph control agent higher, major diameter of preparing heat decomposition temperature under the conditions of constant pressure hydro-thermal in the salting liquid containing sodium ion
Than relatively low short and thick shape α-hemihydrate calcium sulfate crystal whisker, and the reinforcing agent in this, as rigid plastics and infrared function of heat reflection filler,
Mechanics and heat-proof quality to rigid plastics carry out functional modification, and discarded object is carried out into higher value application, and it is more that low cost can be achieved
Functionalization, reduce rigid plastics and be modified cost.
Embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the content of the invention and not only
It is limited only to the following examples.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present invention and PVC rigid plastics adds double screw extruder
Extruding pelletization is carried out, produces tough-increased and reinforced modification plastics.Specifically, during the extruding pelletization, screw speed be 120-300 turn/
Minute, temperature is 170-220 DEG C.
Embodiment 1
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 5-10 μm, draw ratio 1-6, preparation method is as follows：Point
The K that NaCl solution, concentration that concentration is 30wt20wt% are 20wt% is not prepared2SO4Solution, by both by volume
3：Poured into after 1 mixing in reactor；Then toward addition ardealite in reactor and crystal polymorph control agent (sodium citrate and grape acid
The mixture of sodium, sodium citrate and sodium gluconate quality proportioning scope control are 2：1) reaction temperature, is set as 95 DEG C, water-bath
Heating, after isothermal reaction 5 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half-H 2 O calcium sulphate
Whisker.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The addition of crystal polymorph control agent is ardealite matter
The 0.10% of amount.
Above-mentioned preparation method of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics, comprise the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 5-10 μ ms, draw ratio 1-6；By mass, 7g methyl is weighed
Butyl acrylate, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g sodium hydrogensulfites-potassium peroxydisulfate
(oxidant is 1.2 with reducing agent mol ratio to redox initiation system：1), before dispersant, emulsifying agent, initiator and elasticity
Drive body and be divided into two batches；
(2) the KH-550 acetone solns of mass fraction 5% are prepared, are discharged after calcium sulfate crystal whiskers are added thereto into mixing, are dried
Modified calcium sulfate crystal whiskers are obtained afterwards；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 80 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 6 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtain calcium sulfate crystal whiskers-polybutyl methacrylate butyl methacrylate elastomeric precursors
(elastomer or elastomeric precursors, thinking personally it is polybutyl methacrylate elastomer An elastomer) 2.5g compound middle breast
Liquid seed；
(4) weigh and methacrylic acid fourth is added in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate
Ester (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system and 500mL
Deionized water carries out graft polymerization reaction again, then in N270 DEG C of reaction temperature, constant temperature are warming up to while protection, stirring
Stirring 6 hours, calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure is generated, be then cooled to room temperature, add CaCl2
It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers/elastomer
Core shell structure particle, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present invention and PVC rigid plastics adds double screw extruder
Extruding pelletization is carried out, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.Tool
Body, during the extruding pelletization, screw speed is 200 revs/min, and temperature is 180 DEG C.
The toughness reinforcing enhancing and whisker modified dose of the gypsum base of heat-proof quality that this embodiment is prepared make PVC in 23 DEG C of shock strengths
Than lifting >=30% before modified, and tough-increased and reinforced modification cost reduces by 40%, in addition modified hard plastic products hemispherical reflectivity, hair
Penetrate rate >=80%, the heat-insulated temperature difference >=10 DEG C.
Embodiment 2
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 4-8 μm, draw ratio 2-8, preparation method is as follows：
The CaCl that NaCl solution, concentration that concentration is 25wt% are 25wt% is prepared respectively2Solution, will both by volume 3：1
Poured into after mixing in reactor；Then toward addition ardealite and crystal polymorph control agent in reactor, reaction temperature is set as 95 DEG C,
Heating water bath, after isothermal reaction 5 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half water sulphur
Sour calcium pyroborate.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The addition of crystal polymorph control agent is phosphorus stone
The 0.10% of cream quality.
The preparation method of the above-mentioned crystal whisker reinforced and toughened plastics of modified gypsum base, comprises the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 4-8 μ ms, and draw ratio is in the range of 2-8；By mass, weigh
7g butyl methacrylates, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g sodium hydrogensulfites-
(oxidant is 1 with reducing agent mol ratio to potassium persulfate oxidation reduction system：1), dispersant, emulsifying agent, initiator and elasticity
Presoma is divided into two batches；
(2) the KH-560 acetone solns of mass fraction 5% are prepared, discharges, obtains after calcium sulfate crystal whiskers are added thereto into mixing
Modified calcium sulfate crystal whiskers solution；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 70 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 5 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtain the compound of calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors 2.5g
Intermediate emulsion seed；
(4) weigh in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors and add first
Base butyl acrylate (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system with
And 500mL deionized waters carry out graft polymerization reaction again, then in N2Reaction temperature is warming up to while protection, stirring
60 DEG C, constant temperature stirs 5 hours, generates calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure, is then cooled to room temperature,
Add CaCl2It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers
The core shell structure particle of/elastomer, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present embodiment and PVC rigid plastics adds twin-screw extrusion
Machine carries out extruding pelletization, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.
Specifically, during the extruding pelletization, screw speed is 220 revs/min, and temperature is 200 DEG C.
Embodiment 3
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 3-6 μm, draw ratio 1-9, preparation method is as follows：
The CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2Solution, will both by volume 1：1
Poured into after mixing in reactor；Then toward addition ardealite and crystal polymorph control agent in reactor, reaction temperature is set as 95 DEG C,
Heating water bath, after isothermal reaction 4 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half water sulphur
Sour calcium pyroborate.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:8；The addition of crystal polymorph control agent is phosphorus stone
The 0.10% of cream quality.
The preparation method of the above-mentioned crystal whisker reinforced and toughened plastics of modified gypsum base, comprises the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 3-6 μ ms, and draw ratio is in the range of 1-9；By mass percentage
Meter, it is sub- to weigh 7g butyl methacrylates, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g
(oxidant is 1.1 with reducing agent mol ratio to niter cake-potassium persulfate oxidation reduction system：1), dispersant, emulsifying agent, draw
Hair agent and elastomeric precursors are divided into two batches；
(2) the KH-560 acetone solns of mass fraction 5% are prepared, discharges, obtains after calcium sulfate crystal whiskers are added thereto into mixing
Modified calcium sulfate crystal whiskers solution；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 80 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 4 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtaining calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors, (2.5g's answers
Close intermediate emulsion seed；
(4) weigh in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors and add first
Base butyl acrylate (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system with
And 500mL deionized waters carry out graft polymerization reaction again, then in N2Reaction temperature is warming up to while protection, stirring
70 DEG C, constant temperature stirs 4 hours, generates calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure, is then cooled to room temperature,
Add CaCl2It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers
The core shell structure particle of/elastomer, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present embodiment and PVC rigid plastics adds twin-screw extrusion
Machine carries out extruding pelletization, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.
Specifically, during the extruding pelletization, screw speed is 190 revs/min, and temperature is 200 DEG C.
Embodiment 4
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 5-10 μm, draw ratio 1-6, preparation method is as follows：
The CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2Solution, will both by volume 3：1
Poured into after mixing in reactor；Then toward addition ardealite and crystal polymorph control agent in reactor, reaction temperature is set as 85 DEG C,
Heating water bath, after isothermal reaction 4 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half water sulphur
Sour calcium pyroborate.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:8；The addition of crystal polymorph control agent is phosphorus stone
The 0.05% of cream quality.
The preparation method of the above-mentioned crystal whisker reinforced and toughened plastics of modified gypsum base, comprises the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 3-6 μ ms, and draw ratio is in the range of 1-9；By mass percentage
Meter, it is sub- to weigh 7g butyl methacrylates, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g
(oxidant is 1.1 with reducing agent mol ratio to niter cake-potassium persulfate oxidation reduction system：1), dispersant, emulsifying agent, draw
Hair agent and elastomeric precursors are divided into two batches；
(2) the KH-560 acetone solns of mass fraction 4% are prepared, discharges, obtains after calcium sulfate crystal whiskers are added thereto into mixing
Modified calcium sulfate crystal whiskers solution；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 70 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 6 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtain calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors .5g compound centre
Emulsion seed；
(4) weigh in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors and add first
Base butyl acrylate (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system with
And 500mL deionized waters carry out graft polymerization reaction again, then in N2Reaction temperature is warming up to while protection, stirring
60 DEG C, constant temperature stirs 6 hours, generates calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure, is then cooled to room temperature,
Add CaCl2It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers
The core shell structure particle of/elastomer, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present embodiment and PVC rigid plastics adds twin-screw extrusion
Machine carries out extruding pelletization, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.
Specifically, during the extruding pelletization, screw speed is 190 revs/min, and temperature is 180 DEG C.
Embodiment 5
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 4-8 μm, draw ratio 2-8, preparation method is as follows：
The CaCl that NaCl solution, concentration that concentration is 25wt% are 25wt% is prepared respectively2Solution, will both by volume 2：1
Poured into after mixing in reactor；Then toward addition ardealite and crystal polymorph control agent in reactor, reaction temperature is set as 95 DEG C,
Heating water bath, after isothermal reaction 5 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half water sulphur
Sour calcium pyroborate.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:8；The addition of crystal polymorph control agent is phosphorus stone
The 0.05% of cream quality.
The preparation method of the above-mentioned crystal whisker reinforced and toughened plastics of modified gypsum base, comprises the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 4-8 μ ms, and draw ratio is in the range of 2-8；By mass percentage
Meter, it is sub- to weigh 7g butyl methacrylates, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g
(oxidant is 1.2 with reducing agent mol ratio to niter cake-potassium persulfate oxidation reduction system：1), dispersant, emulsifying agent, draw
Hair agent and elastomeric precursors are divided into two batches；
(2) the KH-560 acetone solns of mass fraction 4% are prepared, discharges, obtains after calcium sulfate crystal whiskers are added thereto into mixing
Modified calcium sulfate crystal whiskers solution；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 80 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 4 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtain calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors 2.5g compound centre
Emulsion seed；
(4) weigh in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors and add first
Base butyl acrylate (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system with
And 500mL deionized waters carry out graft polymerization reaction again, then in N2Reaction temperature is warming up to while protection, stirring
70 DEG C, constant temperature stirs 6 hours, generates calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure, is then cooled to room temperature,
Add CaCl2It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers
The core shell structure particle of/elastomer, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present embodiment and PVC rigid plastics adds twin-screw extrusion
Machine carries out extruding pelletization, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.
Specifically, during the extruding pelletization, screw speed is 180 revs/min, and temperature is 200 DEG C.
Embodiment 6
A kind of modified gypsum base whisker for activeness and quietness plastics, using calcium sulfate crystal whiskers as kernel, polybutyl methacrylate bullet
Property body be external coating core shell structure, can be used in PVC functional modification.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, for diameter at 3-6 μm, draw ratio 1-9, preparation method is as follows：
The CaCl that NaCl solution, concentration that concentration is 30wt% are 30wt% is prepared respectively2Solution, will both by volume 1：1
Poured into after mixing in reactor；Then toward addition ardealite and crystal polymorph control agent in reactor, reaction temperature is set as 85 DEG C,
Heating water bath, after isothermal reaction 4 hours, filter while hot, filter cake is placed on into vacuum drying chamber dries, and is dried to obtain α-half water sulphur
Sour calcium pyroborate.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The addition of crystal polymorph control agent is phosphorus stone
The 0.05% of cream quality.
The preparation method of the above-mentioned crystal whisker reinforced and toughened plastics of modified gypsum base, comprises the following steps：
(1) calcium sulfate crystal whiskers are chosen, diameter is in 3-6 μ ms, and draw ratio is in the range of 1-9；By mass percentage
Meter, it is sub- to weigh 7g butyl methacrylates, 3g calcium sulfate crystal whiskers, 3.4g isobutanols, 4g neopelexes, 1g
(oxidant is 1.1 with reducing agent mol ratio to niter cake-potassium persulfate oxidation reduction system：1), dispersant, emulsifying agent, draw
Hair agent and elastomeric precursors are divided into two batches；
(2) the KH-560 acetone solns of mass fraction 4% are prepared, discharges, obtains after calcium sulfate crystal whiskers are added thereto into mixing
Modified calcium sulfate crystal whiskers solution；
(3) elastomeric precursors butyl methacrylate (BMA) 3.5g and modified α-hemihydrate calcium sulfate crystal whisker 3g are mixed
Together in 500mL deionized waters, and add isobutanol 1.7g, neopelex (SDBS) 2g, sodium hydrogensulfite
It is fully dispersed through magnetic stirrer stirring 10min after-potassium peroxydisulfate system 0.5g, then in N2Heated up while protection, stirring
To 70 DEG C of reaction temperature, carry out graft polymerization reaction and stop reaction, cooling discharge, CaCl after 6 hours2Solution is demulsified, vacuum
Filter and 12h is dried at 100 DEG C, obtain calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors 2.5g compound centre
Emulsion seed；
(4) weigh in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-polybutyl methacrylate elastomeric precursors and add first
Base butyl acrylate (BMA) 3.5g, neopelex (SDBS) 2g, sodium hydrogensulfite-potassium peroxydisulfate system with
And 500mL deionized waters carry out graft polymerization reaction again, then in N2Reaction temperature is warming up to while protection, stirring
50 DEG C, constant temperature stirs 6 hours, generates calcium sulfate crystal whiskers/elastomer composite emulsion of core/shell structure, is then cooled to room temperature,
Add CaCl2It is demulsified, after vacuum filtration, is dried 10 hours at 100 DEG C, grinding obtains white powder, obtains calcium sulfate crystal whiskers
The core shell structure particle of/elastomer, i.e. the modified gypsum base whisker for activeness and quietness plastics.
Gained is used for the modified gypsum base whisker of activeness and quietness plastics in the present embodiment and PVC rigid plastics adds twin-screw extrusion
Machine carries out extruding pelletization, produces the tough-increased and reinforced modification PVC material of polybutyl methacrylate elastomer cladding crystal whisker of gypsum.
Specifically, during the extruding pelletization, screw speed is 200 revs/min, and temperature is 220 DEG C.
Equally, the modified gypsum base whisker for the activeness and quietness PVC plastic that embodiment 2-6 is prepared changes in 23 DEG C of shock strength ratios
Property before lifted >=30%, and tough-increased and reinforced modification cost reduce about 40%, in addition modified hard plastic products hemispherical reflectivity, transmitting
Rate >=80%, the heat-insulated temperature difference >=10 DEG C.
The present invention is that the calcium sulfate crystal whiskers of ideal dimensions are added in PVC polymer, and whisker surface is through before hydrophobic modified and elastic
Body polymerization cladding is driven, the elastomer coated inorganic rigid particle structure of formation, mechanics and heat-proof quality to PVC plastic are carried out
Functional modification, there is excellent activeness and quietness effect.
Described above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of not departing from the invention design, some modifications and variations can also be made, these belong to the protection model of the present invention
Enclose.
Claims (10)
1. a kind of modified gypsum base whisker for activeness and quietness plastics, it is characterised in that it is brilliant with the calcium sulfate after hydrophobic treatment
It must be kernel, the core shell structure that polymer elastomer is external coating.
2. a kind of modified gypsum base whisker for activeness and quietness plastics according to claim 1, it is characterised in that described
Elastomer is polybutyl methacrylate.
3. a kind of modified gypsum base whisker for activeness and quietness plastics according to claim 1, it is characterised in that described
For Calcium Sulfate Whiskers in 1-10 μ ms, draw ratio is no more than 10.
4. a kind of modified gypsum base whisker for activeness and quietness plastics according to claim 1, it is characterised in that described
Calcium sulfate crystal whiskers are prepared with the following method：Prepare mass fraction 20%-30% heat stabilizer solution, add ardealite and
4-6 hours are reacted in crystal polymorph control agent under the conditions of 80-95 DEG C of normal pressure, then filter while hot, will be α-half water after filtration cakes torrefaction
Calcium sulfate crystal whiskers；Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:(4~8)；The addition of crystal polymorph control agent
For the 0.05-0.15% of phosphogypsum quality.
5. a kind of modified gypsum base whisker for activeness and quietness plastics according to claim 4, it is characterised in that described
Whisker heat stabilizer solution is the NaCl solution and K that mass fraction is 20%-30%2SO4Solution presses 1:(0.1-10) volume
Mixed preparing forms；Or the whisker heat stabilizer solution is the NaCl solution and CaCl that mass fraction is 20%-30%2
Solution presses 1:(0.1-10) volume mixture is formulated；The crystal polymorph control agent is the mixture of sodium citrate and sodium gluconate,
Sodium citrate and sodium gluconate quality proportioning scope control are 1：(0.1~10).
A kind of 6. preparation method of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics, it is characterised in that bag
Include following steps：
(1) calcium sulfate crystal whiskers are chosen, for diameter in 1-10 μ ms, draw ratio is no more than 10；By mass percentage,
Weigh elastomeric precursors 35-40%, calcium sulfate crystal whiskers 12-20%, dispersant 15-23%, emulsifying agent 18-25%, initiator 3-
5%；Dispersant, emulsifying agent, initiator, elastomeric precursors are divided into two batches；
(2) mass fraction 3%-5% KH-550 acetone solns are prepared, are discharged after calcium sulfate crystal whiskers are added thereto into mixing,
Modified calcium sulfate crystal whiskers are obtained after drying；
(3) elastomeric precursors and modified calcium sulfate crystal whiskers are mixed in water, and add part dispersant, emulsifying agent,
Heating water bath carries out graft polymerization reaction after initiator is well mixed, is demulsified, filters, dries after the completion of reaction, obtains calcium sulfate
The compound intermediate emulsion seed of whisker-elastomer；
(4) dispersant of surplus, emulsifying agent will be added in the compound intermediate emulsion seed of gained calcium sulfate crystal whiskers-elastomer, drawn
Hair agent, elastomeric precursors and water carry out graft polymerization reaction again, generate calcium sulfate crystal whiskers/elastomer composite breast of core/shell structure
Liquid, then through demulsification, suction filtration and drying steps, the core shell structure particle of calcium sulfate crystal whiskers/elastomer is obtained, that is, is used to strengthen
The modified gypsum base whisker of toughened plastics.
A kind of 7. system of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics according to claim 6
Preparation Method, it is characterised in that one or more of the dispersant in isobutanol, polyvinyl alcohol；The emulsifying agent is selected from ten
One or more in dialkyl benzene sulfonic acids sodium, dodecyl sodium sulfate；The initiator is selected from redox system initiator,
By mass percentage, oxidant and reducing agent mol ratio are (1~1.2)：1.
A kind of 8. system of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics according to claim 6
Preparation Method, it is characterised in that the elastomeric precursors are butyl methacrylate.
A kind of 9. system of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics according to claim 6
Preparation Method, it is characterised in that dispersant, emulsifying agent, initiator and elastomeric precursors are divided into two batches, first batch and second
Batch dosage mass ratio is 1：2~3.
A kind of 10. system of the modified gypsum base whisker based on emulsion polymerization for activeness and quietness plastics according to claim 6
Preparation Method, it is characterised in that the graft polymerization reaction condition in the step (3) is：Under inert atmosphere, polymerization temperature control
At 70-80 DEG C, polymerization time was controlled in 4-6 hours；Graft polymerization reaction condition in the step (4) is：Inert atmosphere
Under, at 50-70 DEG C, polymerization reaction time was controlled in 4-6 hours for polymerization temperature control.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485808A (en) * | 2018-11-27 | 2019-03-19 | 黔南民族师范学院 | A kind of ardealite grafted polystyrene polymer and preparation method thereof |
| CN114106271A (en) * | 2021-12-24 | 2022-03-01 | 贵州大学 | Preparation method of polymer grafted and coated anhydrous phosphogypsum composite microspheres |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010552A (en) * | 2010-11-29 | 2011-04-13 | 上海工程技术大学 | Polyvinyl chloride (PVC)/whisker calcium sulfate composite material and preparation method thereof |
| CN102134358A (en) * | 2011-05-03 | 2011-07-27 | 刘立文 | Calcium sulfate whisker-modified polyvinyl chloride composite material and preparation process thereof |
| CN102603219A (en) * | 2012-03-16 | 2012-07-25 | 武汉理工大学 | Process for preparing high-activity semi-hydrated gypsum cementing material and gypsum product by aid of phosphorous gypsum |
| CN103102563A (en) * | 2012-11-13 | 2013-05-15 | 合肥朗胜新材料有限公司 | EPDM (Ethylene-propylene-diene monomer) coated calcium sulfate whisker modified LDPE (low-density polyethylene) foam material and preparation method thereof |
| CN103497391A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | Calcium sulfate crystal whisker master batch and method for preparing same |
-
2016
- 2016-05-06 CN CN201610294668.0A patent/CN107344990A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010552A (en) * | 2010-11-29 | 2011-04-13 | 上海工程技术大学 | Polyvinyl chloride (PVC)/whisker calcium sulfate composite material and preparation method thereof |
| CN102010552B (en) * | 2010-11-29 | 2012-05-30 | 上海工程技术大学 | Polyvinyl chloride (PVC)/whisker calcium sulfate composite material and preparation method thereof |
| CN102134358A (en) * | 2011-05-03 | 2011-07-27 | 刘立文 | Calcium sulfate whisker-modified polyvinyl chloride composite material and preparation process thereof |
| CN102603219A (en) * | 2012-03-16 | 2012-07-25 | 武汉理工大学 | Process for preparing high-activity semi-hydrated gypsum cementing material and gypsum product by aid of phosphorous gypsum |
| CN103102563A (en) * | 2012-11-13 | 2013-05-15 | 合肥朗胜新材料有限公司 | EPDM (Ethylene-propylene-diene monomer) coated calcium sulfate whisker modified LDPE (low-density polyethylene) foam material and preparation method thereof |
| CN103497391A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | Calcium sulfate crystal whisker master batch and method for preparing same |
Non-Patent Citations (5)
| Title |
|---|
| YUAN WENJING，等: "A novel surface modification for calcium sulfate whisker used for reinforcement of poly(vinylchloride)", 《JOURNAL OF POLYMER RESEARCH》 * |
| 孙传尧: "《选矿工程师手册（第2册）上卷：选矿通论》", 31 March 2015, 冶金工业出版社 * |
| 江苏一夫科技股份有限公司编撰: "《工业副产石膏研究报告汇编》", 31 January 2014, 中国建材工业出版社 * |
| 王少会: "原位聚合制备核壳结构甲基丙烯酸甲酯/硫酸钙复合粒子的应用", 《化工新型材料》 * |
| 郭泰民编: "《工业副产石膏应用技术》", 30 October 2010, 中国建材工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485808A (en) * | 2018-11-27 | 2019-03-19 | 黔南民族师范学院 | A kind of ardealite grafted polystyrene polymer and preparation method thereof |
| CN114106271A (en) * | 2021-12-24 | 2022-03-01 | 贵州大学 | Preparation method of polymer grafted and coated anhydrous phosphogypsum composite microspheres |
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