CN108164902A - Modified montmorillonite used dispersion liquid, 3D printing dusty material and preparation method thereof - Google Patents
Modified montmorillonite used dispersion liquid, 3D printing dusty material and preparation method thereof Download PDFInfo
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- CN108164902A CN108164902A CN201810076909.3A CN201810076909A CN108164902A CN 108164902 A CN108164902 A CN 108164902A CN 201810076909 A CN201810076909 A CN 201810076909A CN 108164902 A CN108164902 A CN 108164902A
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- C08K9/00—Use of pretreated ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- 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
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- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of modified montmorillonite used dispersion liquids, 3D printing dusty material and preparation method thereof, the preparation method of the 3D printing dusty material includes 100~200 parts of soft monomers, 100~200 parts of hard monomers and 50~100 parts of function monomers are stirred to and are warming up to 60~90 DEG C, 50~150 parts of modified montmorillonite used dispersion liquids are slowly added dropwise, then proceed to insulation reaction, product obtained by the reaction is filtered afterwards again, it is dry.The 3D printing dusty material of the present invention is obtained by using modified montmorillonite used dispersion liquid modified polyacrylate resin, not only environmentally protective, but also can be printed with it to obtain the entity finished product for having excellent flexibility, high bond strength, high printing precision.
Description
Technical field
The present invention relates to printed material technical field, in particular to a kind of modified montmorillonite used dispersion liquid and its preparation
Method, 3D printing dusty material and preparation method thereof and 3D printing material.
Background technology
One kind of 3D printing technique, that is, rapid shaping technique, based on digital model file, with dusty material and
Jointing material carrys out constructed object by layer-by-layer printing.There is many different technologies for 3D printing technique.They are not
It is in a manner of available material with part, and with different layer building establishment portion parts.3D printing technique is in biomedical, work
Many industries such as industry manufacture, aerospace, automobile, building are used widely.
3D printing material includes dusty material and binding material (also referred to as " bonding solution "), they are to realize 3D printing skill
The key of art.There are also for example the companies such as U.S. 3D Systems successfully develop external existing commercialized 3D printing material
Metal, plastics, starch, composite material etc..But cost-effective 3D printing material is in short supply at present, very rare and printing
It is ineffective.The country, still in the starting stage, is very different in terms of 3D printing material development exploitation with foreign level.Therefore,
3D printing material environmentally protective, cost-effective, that printing effect excellent of the exploitation with independent intellectual property right shows with important
Sincere justice and actual application value.
Invention content
In view of this, a kind of modified montmorillonite used dispersion liquid provided by the invention and preparation method thereof, 3D printing dusty material
And preparation method thereof and 3D printing material, preferably overcome the above-mentioned problems of the prior art and defect, the 3D printing powder
Powder material is obtained by using modified montmorillonite used dispersion liquid modified polyacrylate resin, and can directly by the use of water as bond material
Material coordinates the 3D printing dusty material to obtain 3D printing material, not only environmentally protective, but also can be printed and be had with it
Excellent flexibility, high bond strength, high printing precision entity finished product.
A kind of preparation method of modified montmorillonite used dispersion liquid, including：
By 100 parts of montmorillonites and 5~20 parts of rare earth oxides after mixing, it then roasts；
20~50 parts of organic quaternary ammonium salts of addition to be cooled to room temperature and 1000~3000 parts of water are uniformly mixed；
5~15 parts of hydrogen peroxide are continuously added to be uniformly mixed.
Further, the temperature of the roasting is 150~250 DEG C；The time of the roasting is 15~30min.
Further, the rare earth oxide is lanthanum sesquioxide, cerium sesquioxide, ceria, yttria, three
Aoxidize at least one of two neodymiums.
Further, the organic quaternary ammonium salt is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, ten
At least one of eight alkyl trimethyl ammonium bromides, octadecyltrimethylammonium chloride.
The present invention also provides a kind of modified montmorillonite used dispersion liquid, the modified montmorillonite used dispersion liquid is by above-mentioned modified illiteracy
The preparation method of de- stone dispersion liquid is prepared.
The present invention also provides a kind of preparation method of 3D printing dusty material, including：
100~200 parts of soft monomers, 100~200 parts of hard monomers and 50~100 parts of function monomers are stirred and heated up
To 60~90 DEG C, 1000~2000 parts of modified montmorillonite used dispersion liquids are slowly added dropwise, then proceed to insulation reaction, then will react afterwards
The product filtering arrived, it is dry；
The modified montmorillonite used dispersion liquid is above-mentioned modified montmorillonite used dispersion liquid；
The soft monomer is at least one of methyl acrylate, ethyl acrylate and butyl acrylate；
The hard monomer is at least one of styrene, methyl methacrylate and ethyl methacrylate；
The function monomer is at least one of acrylic acid and methacrylic acid.
Further, the time control that modified montmorillonite used dispersion liquid is added dropwise is 0.5~1.5h；During the insulation reaction
Between be 2~5h.
Further, it before the drying, further includes and the product after filtering is washed.
The present invention also provides a kind of preparation method of 3D printing dusty material, the 3D printing dusty material is above-mentioned
The preparation method of 3D printing dusty material is prepared.
The present invention also provides a kind of preparation method of 3D printing material, including 3D printing dusty material and adhesives,
The mass ratio of the 3D printing dusty material and the adhesives is 10：0.5~1.5；The 3D printing dusty material is upper
The 3D printing dusty material stated, the adhesives are water.
Compared with prior art, a kind of modified montmorillonite used dispersion liquid of the invention and preparation method thereof, 3D printing powder material
Material and preparation method thereof and the advantageous effect of 3D printing material are：
(1) present invention makes the rare earth member in rare earth oxide first by being roasted after montmorillonite and rare earth oxide mixing
Element penetrates into Si-O tetrahedrons and Al-O dioctahedrons in montmorillonite layer-lattice structure, while montmorillonite dioctahedron is to three or eight
Face body mistake, both (such as you were de- with conventional dioctahedron smectite minerals for the obtained layer-lattice structure of rare earth oxide/montmorillonite
Stone etc.) it is different, it is also different with conventional trioctahedron smectite minerals (such as hectorite, magnesium smelting)：Be for its upper and lower two layers rare earth/
Si-O tetrahedrons, one layer of centre folder are rare earth/Al-O structures in transition state between dioctahedron and trioctahedron；The tool
Rare earth oxide/montmorillonite of standby special transition layer-lattice structure is again with generating microcapsule structure after organic quaternary ammonium reactant salt
Quaternary ammonium salt-modified rare earth oxide/montmorillonite not only shows the hydrophobic oleophilic oil performance identical with conventional organobentonite, but also
Have excellent emulsion dispersion function, make it with need not additionally use emulsifier during acrylic resin polymerisation；In addition, peroxide
Changing hydrogen molecule can enter in microcapsules and in relatively stable state.In polymerisation, hydrogen peroxide molecule slowly move by diffusion
It removes microcapsules and enters reaction system, due to the unique sustained release performance of microcapsules, so hydrogen peroxide can be decomposed relatively slowly
Into free radical so as to cause acrylate monomer polymerization, therefore entire reaction process is mild, is highly susceptible to controlling, avoids over cure
The normal starters such as sour potassium often occur reacting the shortcomings that violent.
(2) 3D printing dusty material of the invention is obtained using modified montmorillonite used dispersion liquid modified polyacrylate resin,
The effect of wherein soft monomer is to improve the flexility of polymer, so as to increase the flexibility of 3D printing product；The work of hard monomer
Be improve polymer adhesion strength and shear strength, so as to increase the adhesion strength of 3D printing product and shear strength；Work(
Energy monomer introduces carboxyl, so as to which polymer has sufficient amount of-COOH, can be infiltrated under hydrone effect, unfold, twines
Around, therefore 3D printing can be carried out using pure water as adhesives, it is not only environmentally protective, and can print to obtain have it is excellent
Good flexibility, high bond strength, high printing precision entity finished product.
For the above objects, features and advantages of the present invention is enable to be clearer and more comprehensible, preferred embodiment cited below particularly is made detailed
It is described as follows.
Specific embodiment
It is of the invention for the ease of understanding, it elaborates with reference to the mode of embodiment to technical scheme of the present invention,
Many details are elaborated in the following description in order to fully understand the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
Term as used herein：
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.It is wanted for example, composition, step, method, product or device comprising listed elements are not necessarily limited to those
Element, but can include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " by ... form " exclude any element do not pointed out, step or component.If in claim,
This phrase will make claim be closed, it be made not include the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to the element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
All ranges that any pairing of lower limit or preferred value is formed, regardless of whether the range separately discloses.For example, when open
During range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
A kind of preparation method of modified montmorillonite used dispersion liquid, including：
By 100 parts of montmorillonites and 5~20 parts of rare earth oxides after mixing, it then roasts；
20~50 parts of organic quaternary ammonium salts of addition to be cooled to room temperature and 1000~3000 parts of water are uniformly mixed；
5~15 parts of hydrogen peroxide are continuously added to be uniformly mixed.
The parts by weight of above-mentioned rare earth oxide can be enumerated as 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts or 20 parts etc.；
The parts by weight of organic quaternary ammonium salt can be enumerated as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts etc.；The parts by weight of water
Number can be enumerated as 1000 parts, 1200 parts, 1500 parts, 1800 parts, 2000 parts, 2500,2800 parts or 3000 parts etc.；Hydrogen peroxide
Parts by weight can be enumerated as 5 parts, 8 parts, 10 parts, 12 parts or 15 parts etc..
Further, the temperature of the roasting is 150~250 DEG C such as 150 DEG C, 180 DEG C, 200 DEG C, 230 DEG C or 250 DEG C
Deng.
The time of the roasting is 15~30min such as 15min, 18min, 20min, 23min, 25min, 28min or 30min
Deng.
Further, the rare earth oxide is lanthanum sesquioxide, cerium sesquioxide, ceria, yttria, three
Aoxidize at least one of two neodymiums.
Further, the organic quaternary ammonium salt is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, ten
At least one of eight alkyl trimethyl ammonium bromides, octadecyltrimethylammonium chloride.
The present invention also provides a kind of modified montmorillonite used dispersion liquid, the modified montmorillonite used dispersion liquid is by above-mentioned modified illiteracy
The preparation method of de- stone dispersion liquid is prepared.
It should be noted that the present invention makes rare earth oxide first by being roasted after montmorillonite and rare earth oxide mixing
In rare earth element penetrate into Si-O tetrahedrons and Al-O dioctahedrons in montmorillonite layer-lattice structure, while montmorillonite sixteen
Face body to trioctahedron mistake, the obtained layer-lattice structure of rare earth oxide/montmorillonite both with conventional dioctahedron smectite
Mineral (such as montmorillonite) are different, also different with conventional trioctahedron smectite minerals (such as hectorite, magnesium smelting)：Above and below it
Two layers is rare earth/Si-O tetrahedrons, centre folder one layer be between dioctahedron and trioctahedron transition state rare earth/
Al-O structures.
This has rare earth oxide/montmorillonite of special transition layer-lattice structure again with being generated after organic quaternary ammonium reactant salt
Quaternary ammonium salt-modified rare earth oxide/montmorillonite of microcapsule structure not only shows identical with conventional organobentonite hydrophobic
Oleophylic performance, and have excellent emulsion dispersion function, make it with need not additionally use breast during acrylic resin polymerisation
Agent.
In addition, hydrogen peroxide molecule can enter in microcapsules and in relatively stable state.In polymerisation, peroxidating
The slow diffusive migration of hydrogen molecule goes out microcapsules and enters reaction system, due to the unique sustained release performance of microcapsules, so hydrogen peroxide
Free radical can relatively slowly be resolved into so as to cause acrylate monomer polymerization, therefore entire reaction process is mild, very easily
In control, avoid the normal starters such as potassium peroxydisulfate and often occur reacting the shortcomings that violent.
The present invention also provides a kind of preparation method of 3D printing dusty material, including：
100~200 parts of soft monomers, 100~200 parts of hard monomers and 50~100 parts of function monomers are stirred and heated up
To 60~90 DEG C, 1000~2000 parts of modified montmorillonite used dispersion liquids are slowly added dropwise, then proceed to insulation reaction, then will react afterwards
The product filtering arrived, it is dry.
The parts by weight of above-mentioned soft monomer can be enumerated as 100 parts, 120 parts, 150 parts, 180 parts or 200 parts etc.；Hard monomer
Parts by weight can be enumerated as 100 parts, 120 parts, 150 parts, 180 parts or 200 parts etc.；The parts by weight of function monomer can be enumerated as 50
Part, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts etc.；The parts by weight of modified montmorillonite used dispersion liquid can be enumerated as 1000 parts, 1200
Part, 1500 parts, 1800 parts or 2000 parts etc..
The modified montmorillonite used dispersion liquid is above-mentioned modified montmorillonite used dispersion liquid.
The soft monomer is at least one of methyl acrylate, ethyl acrylate and butyl acrylate.
The hard monomer is at least one of styrene, methyl methacrylate and ethyl methacrylate.
The function monomer is at least one of acrylic acid and methacrylic acid.
Further, the time control that modified montmorillonite used dispersion liquid is added dropwise be 0.5~1.5h such as 0.5h, 0.8h, 1h,
1.2h or 1.5h etc..
Further, the insulation reaction time is 2~5h such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h etc..
Further, it before the drying, further includes and the product after filtering is washed.
The present invention also provides a kind of preparation method of 3D printing dusty material, the 3D printing dusty material is above-mentioned
The preparation method of 3D printing dusty material is prepared.
The present invention also provides a kind of preparation method of 3D printing material, including 3D printing dusty material and adhesives,
The mass ratio of the 3D printing dusty material and the adhesives is 10：0.5~1.5 such as 10：0.5、10：0.8、10：1、10：
1.2 or 10：1.5 it waits；The 3D printing dusty material is above-mentioned 3D printing dusty material, and the adhesives is water.
It should be noted that above-mentioned water is both preferably pure water, naturally it is also possible to be deionized water, distilled water or ultra-pure water
Deng.
For the ease of understanding the present invention, the technical solution further illustrated the present invention with reference to embodiment.
Embodiment 1
(1) it after being first uniformly mixed 100 parts of montmorillonites and 5 parts of lanthanum sesquioxides, then is roasted at 150 DEG C
30min, taking-up treat that it is cooled to room temperature and add in 20 parts of cetyl trimethylammonium bromides and 1000 parts of pure water and be sufficiently stirred mixed
Close it is uniform, add in later hydrogen peroxide (contained hydrogen peroxide is 5 parts) that 16.7 parts of mass fractions are 30% and stir evenly to get
To modified montmorillonite used dispersion liquid；
(2) 100 parts of methyl acrylates, 100 parts of styrene, 50 parts of acrylic acid are added in reaction unit, start stirring simultaneously
60 DEG C are warming up to, instills the modified montmorillonite used dispersion liquid prepared by 1000 parts of above-mentioned steps (1) at a slow speed, control time for adding is
0.5h then proceedes to insulation reaction 2h, then stops reaction, and reaction product is filtered and is fully washed with pure water, then fully dry
It is dry to constant weight, that is, Modification of Montmorillonite polyacrylate resin 3D printing dusty material is prepared.
Embodiment 2
(1) after 100 parts of montmorillonites, 10 parts of lanthanum sesquioxides and 10 parts of cerias being uniformly mixed first, then
15min is roasted at 250 DEG C, taking-up treats that it is cooled to room temperature and adds in 25 parts of cetyl trimethylammonium bromides, 25 parts of octadecyls
Trimethylammonium bromide and 3000 parts of pure water simultaneously stir, and add in the hydrogen peroxide that 50.1 parts of mass fractions are 30% later
It (contained hydrogen peroxide be 15 parts) and stirs evenly to get to modified montmorillonite used dispersion liquid；
(2) in reaction unit add in 100 parts of methyl acrylates, 100 parts of ethyl acrylates, 100 parts of styrene, 100 parts
Methyl methacrylate, 50 parts of acrylic acid and 50 parts of methacrylic acids start and stir and be warming up to 90 DEG C, instill 2000 parts at a slow speed
Modified montmorillonite used dispersion liquid prepared by step (1), control time for adding are 1.5h, then proceed to insulation reaction 5h, Zhi Houting
It only reacts, product is filtered and fully washed with pure water, then fully dry to constant weight, that is, Modification of Montmorillonite polyacrylic acid is prepared
Ester resin 3D printing dusty material.
Embodiment 3
(1) 100 parts of montmorillonites, 5 parts of lanthanum sesquioxides, 5 parts of cerias, 5 parts of yttrias are stirred first
After uniformly, then 25min is roasted at 200 DEG C, taking-up treats that it is cooled to room temperature and adds in 10 parts of cetyl trimethylammonium bromides, 15
Part Cetyltrimethylammonium bromide, 5 parts of hexadecyltrimethylammonium chlorides and 2000 parts of pure water simultaneously stir, later
It adds in the hydrogen peroxide (contained hydrogen peroxide is 10 parts) that 33.3 parts of mass fractions are 30% and stirs evenly and taken off to get to modified cover
Stone dispersion liquid；
(2) in reaction unit add in 50 parts of methyl acrylates, 50 parts of ethyl acrylates, 50 parts of butyl acrylates, 50 parts
Styrene, 50 parts of methyl methacrylates, 50 parts of ethyl methacrylate, 20 parts of acrylic acid, 40 parts of methacrylic acids, start and stir
It mixes and is warming up to 80 DEG C, instill the modified montmorillonite used dispersion liquid prepared by 1200 parts of steps (1) at a slow speed, control time for adding is
1h then proceedes to insulation reaction 4h, stops reaction later, and product filters simultaneously fully to be washed with pure water, then fully dry to constant weight,
Modification of Montmorillonite polyacrylate resin 3D printing dusty material is prepared.
Embodiment 4
(1) first by 100 parts of montmorillonites, 4 parts of lanthanum sesquioxides, 4 parts of cerias, 4 parts of yttrias, 3 part of three oxygen
Change after two neodymiums are uniformly mixed, then 20min is roasted at 180 DEG C, taking-up treats that it is cooled to room temperature and adds in 10 parts of cetyls
Trimethylammonium bromide, 10 parts of Cetyltrimethylammonium bromides, 10 parts of hexadecyltrimethylammonium chlorides, 10 parts of octadecyls three
Ammonio methacrylate and 2500 parts of pure water simultaneously stir, and it is (contained to add in the hydrogen peroxide that 40 parts of mass fractions are 30% later
Hydrogen peroxide is 12 parts) and stir evenly to get to modified montmorillonite used dispersion liquid；
(2) in reaction unit add in 40 parts of methyl acrylates, 40 parts of ethyl acrylates, 45 parts of butyl acrylates, 40 parts
Styrene, 40 parts of methyl methacrylates, 55 parts of ethyl methacrylate, 35 parts of acrylic acid and 35 parts of methacrylic acids, start
It stirs and is warming up to 75 DEG C, instill the modified montmorillonite used dispersion liquid prepared by 1500 parts of steps (1) at a slow speed, control time for adding is
1h then proceedes to insulation reaction 3h, stops reaction later, and product filters simultaneously fully to be washed with pure water, then fully dry to constant weight,
Modification of Montmorillonite polyacrylate resin 3D printing dusty material is prepared.
Embodiment 5
(1) 100 parts of montmorillonites, 4 parts of lanthanum sesquioxides, 4 parts of cerias and 4 parts of yttrias are stirred first
After uniformly, then 20min is roasted at 200 DEG C, taking-up treats that it is cooled to room temperature and adds in 8 parts of cetyl trimethylammonium bromides, 11
Part Cetyltrimethylammonium bromide, 11 parts of octadecyltrimethylammonium chloride and 1800 parts of pure water simultaneously stir, it
The hydrogen peroxide (contained hydrogen peroxide is 8 parts) that 26.7 parts of mass fractions are 30% is added in afterwards and is stirred evenly is covered to get to modified
De- stone dispersion liquid；
(2) in reaction unit add in 40 parts of methyl acrylates, 60 parts of ethyl acrylates, 50 parts of butyl acrylates, 60 parts
Styrene, 45 parts of methyl methacrylates, 45 parts of ethyl methacrylate, 40 parts of acrylic acid and 40 parts of methacrylic acids, start
It stirs and is warming up to 75 DEG C, instill the modified montmorillonite used dispersion liquid prepared by 1800 parts of steps (1) at a slow speed, control time for adding is
1h then proceedes to insulation reaction 3.5h, stops reaction later, and product is filtered and fully washed with pure water, then fully dry to perseverance
Weight, that is, be prepared Modification of Montmorillonite polyacrylate resin 3D printing dusty material.
By the printing dusty material prepared by the embodiment of the present invention 1~5 and the similar commodity of import, (U.S. 3D Systems are public
Department's production, model：MPA-3 it is) 10 according to mass ratio with pure water:1 ratio is applied to be printed as entity finished product on 3D printer
And various performance tests are carried out, testing result is as shown in table 1 below.
1 3D printing entity finished product detection result of table
As upper table 1 it is found that as prepared by the embodiment of the present invention 1~5 Modification of Montmorillonite polyacrylate resin 3D printing powder
The performance indicators such as tensile strength, elasticity modulus, elongation at break, the bending strength of the finished product that powder material prints are preferable, table
The entity finished product that the bright 3D printing file printing with the present invention comes out has high bond strength, high printing precision, excellent flexibility,
And performance is more than external similar commodity, therefore prospects for commercial application is wide.
The preferred embodiment of the present invention is above are only, is not intended to restrict the invention, for those skilled in the art
For member, inventive formulation and preparation process can have various modifications and variations.All within the spirits and principles of the present invention, institute
Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified montmorillonite used dispersion liquid, it is characterised in that：Including：
By 100 parts of montmorillonites and 5~20 parts of rare earth oxides after mixing, it then roasts；
20~50 parts of quaternary ammonium salts of addition to be cooled to room temperature and 1000~3000 parts of water are uniformly mixed；
5~15 parts of hydrogen peroxide are continuously added to be uniformly mixed.
2. the preparation method of modified montmorillonite used dispersion liquid according to claim 1, it is characterised in that：The temperature of the roasting
It is 150~250 DEG C；The time of the roasting is 15~30min.
3. the preparation method of modified montmorillonite used dispersion liquid according to claim 1, it is characterised in that：The rare earth oxide
For at least one of lanthanum sesquioxide, cerium sesquioxide, ceria, yttria, neodymium oxide.
4. the preparation method of modified montmorillonite used dispersion liquid according to claim 1, it is characterised in that：The quaternary ammonium salt is ten
Six alkyl trimethyl ammonium bromides, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorine
Change at least one of ammonium.
5. a kind of modified montmorillonite used dispersion liquid, it is characterised in that：The modified montmorillonite used dispersion liquid is by any one of claim 1-4
The preparation method of the modified montmorillonite used dispersion liquid is prepared.
6. a kind of preparation method of 3D printing dusty material, it is characterised in that：Including：
100~200 parts of soft monomers, 100~200 parts of hard monomers and 50~100 parts of function monomers are stirred and are warming up to 60
~90 DEG C, 50~150 parts of modified montmorillonite used dispersion liquids are added dropwise, then proceed to insulation reaction, then afterwards by product mistake obtained by the reaction
Filter, it is dry；
The modified montmorillonite used dispersion liquid is the modified montmorillonite used dispersion liquid described in claim 5；
The soft monomer is at least one of methyl acrylate, ethyl acrylate and butyl acrylate；
The hard monomer is at least one of styrene, methyl methacrylate and ethyl methacrylate；
The function monomer is at least one of acrylic acid and methacrylic acid.
7. the preparation method of 3D printing dusty material according to claim 6, it is characterised in that：Modified cover of the dropwise addition takes off
The time control of stone dispersion liquid is 0.5~1.5h；The insulation reaction time is 2~5h.
8. the preparation method of 3D printing dusty material according to claim 6, it is characterised in that：Before the drying,
It further includes and the product after filtering is washed.
9. a kind of 3D printing dusty material, it is characterised in that：The 3D printing dusty material is any one of claim 6~8 institute
The preparation method of 3D printing dusty material stated is prepared.
10. a kind of 3D printing material, it is characterised in that：Including 3D printing dusty material and adhesives, the 3D printing powder
The mass ratio of material and the adhesives is 10：0.5~1.5；The 3D printing dusty material is the 3D described in claim 9
Dusty material is printed, the adhesives is water.
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| CN109782537B (en) * | 2019-03-07 | 2022-05-20 | 中山职业技术学院 | Preparation method of 3D printing type negative photoresist for high-precision semiconductor |
| CN116891596A (en) * | 2023-07-25 | 2023-10-17 | 铨盛聚碳科技股份有限公司 | Flame retardant containing rare earth sulfonate intercalation inorganic matter and preparation method thereof |
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Application publication date: 20180615 |