CN109337013A - A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method - Google Patents
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method Download PDFInfo
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- CN109337013A CN109337013A CN201811137706.7A CN201811137706A CN109337013A CN 109337013 A CN109337013 A CN 109337013A CN 201811137706 A CN201811137706 A CN 201811137706A CN 109337013 A CN109337013 A CN 109337013A
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- cyclodextrin
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/1305—Organic additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6344—Copolymers containing at least three different monomers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The present invention relates to a kind of cyclodextrin copolymers ceramic green body reinforcing agents modified based on ATRP method, modified cyclodextrin monomer containing double bonds is first prepared, then is polymerized using the acrylate monomer of aqueous ATRP method initiation modified cyclodextrin monomer, acrylate monomers, hydroxyl；The present invention proposes that a kind of cyclodextrin copolymers ceramic green body reinforcing agent preparation method modified based on ATRP method, the number-average molecular weight of the cyclodextrin copolymers ceramic green body reinforcing agent are 15000~25000, PDI≤1.3.Ceramic green body reinforcing agent of the invention has high hydroxyl content using cyclodextrin, hydroxy-acrylate monomer as repetitive unit, and strong hydrogen bonding effect can occur with green body pulp particle；Due to the special peviform structure of cyclodextrin, winding and cladding are formed to green body pulp particle, reinforcing effect is more efficient；And there is good dispersibility, and it is small to the viscosity influence of green body slurry, without additional addition degumming agent.
Description
Technical field
The present invention relates to a kind of preparation method of ceramics reinforcing agent more particularly to a kind of ring pastes modified based on ATRP method
Smart copolymer ceramic green body reinforcing agent, belongs to ceramics reinforcing agent synthesis technical field.
Background technique
In ceramic wall and floor bricks production, the phenomenon that generally existing ceramics ligand intensity is poor, and breakage rate is high, usually by raising
The briquetting pressure of press increases intensity, press pressure to a certain extent after, it is to the effect for improving ligand intensity unobvious, be full
Each technique of foot requires often to need to be added different additives, while can reduce the expense and energy consumption of molding equipment, energy saving economy, greatly
The big intensity for improving ceramic ligand.Although dosage is little, play an important role, wherein it is dry-pressing formed due to using, with
The increase of product specification, requirements at the higher level are proposed to Ceramic Tiles blank strength.If blank strength is insufficient, cause green body at
Generated in the technical process such as shape, conveying, drying, glazing it is damaged, breakage rate up to 10~20%, seriously constrain production efficiency and
The raising of product quality.
To increase the intensity of ceramic body, first is that improving the good clay content of plasticity in green body, mention blank strength
Height, but also increase the dry of green body simultaneously and shrink, firing shrinks and improves firing temperature etc.；Second is that being added in formula
Suitable reinforcing agent；Reinforcing agent is also known as temporary adhesive, and reinforcing agent is mostly organic high molecular polymer or solution, mainly benefit
With the crosslinked action of molecule long-chain, ceramic particle is surrounded and connected, particle is prevented to generate displacement under stress condition, from
And play reinforcing effect.Since the reinforcing agent molecular weight of high score subclass is larger, structural chain is longer, will be various fine in mud
When feed particles flock together, it also will form reticular structure and wrap Free water in mud, the mobility of mud is made to be deteriorated,
Addition is more, and the mobility of mud is also poorer, only increases additional water in production in mud to solve the above-mentioned problems, this
The specific gravity of sample mud reduces, and water content increases, and the energy consumption of mist projection granulating is consequently increased, it is therefore desirable to liquefacient be added to reduce
The viscosity of mud reduces the moisture content of mud to reduce fuel consumed by dry slime water point in spray tower granulating working procedure.
Chinese patent CN104530318A discloses a kind of acrylamide graft cornstarch ceramics reinforcing agent and its preparation
Methods and applications, the invention is with starch for main synthesis material, and source is wide, pollution-free, and relatively other reinforcing agents more clean, is green
Color；When overcoming native starch poor processability, low temperature difficulty dispersion and penetrating power is poor and polyacrylamide is on the high side,
The pollution of residual monomer, using being limited by various conditions the disadvantages of；Starch pre-gelatinized is easy to operate, grafting synthesis technology letter
It is single, it is easy to accomplish industrialized production.But due to the invention reinforcing agent with cornstarch be main enhancing ingredients, it is big that there are additive amounts
The shortcomings that；It is polymerize when simultaneously synthesizing using conventional free radical, reinforcing agent molecular weight distribution is wider, and performance is unstable.
Summary of the invention
Performance existing for existing ceramic green body reinforcing agent is unstable, the wider disadvantage of molecular weight distribution to overcome, the present invention
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method is provided.
The ATRP method, i.e. Transfer Radical Polymerization, it can be achieved that free radical controllable polymerization, the polymerization prepared
Object has the characteristics that molecular weight is controllable, narrow molecular weight distribution.
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method of the present invention, molecular structural formula
It is as follows:
In molecular formula, the R1、R2、R3For-H ,-CH3Or-CH2CH3；The M is Na+、K+Or NH4 +；N=2~4,
X=6~10, y=5~10, z=15~30；Its number-average molecular weight of the ceramic green body reinforcing agent is 15000~25000, PDI
≤1.3。
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, preparation step are as follows:
A) according to parts by weight, by 20.0 parts of cyclodextrins in 40.0 parts of DMSO, 60~70 DEG C are heated under stirring,
1.5~4.0 parts of activated monomers containing double bonds are added dropwise dropwise, is added dropwise in 0.5~1h, then continues at 60~70 DEG C
8~13h is reacted, room temperature is cooled to, methanol dilution is added with acetone precipitation, micro- light yellow solid is obtained by filtration, then washed with acetone
It washs 3 times, obtains the modified cyclodextrin monomer of light yellow solid；
B) successively by 30.0~40.0 parts of acrylate monomers, 10.0~15.0 parts of hydroxyls acrylate monomer,
30.0~40.0 parts of modified cyclodextrin monomers, 0.1~1.0 part of ligand, 0.5~2.5 part of catalyst, 0.1~0.3 part of surface-active
Agent and 100.0~150.0 parts of deionized waters are added in reactor, are warming up to 60~90 DEG C after stirring and dissolving, it is added dropwise 5.0~
10.0 parts of 15% part of initiator solutions, are added dropwise in 0.5~1h, and 1h~3h is then reacted at 60~90 DEG C, cooling
Filtering, filter cake is washed, dry, granulation, packs, and obtains a kind of cyclodextrin copolymers ceramic body modified based on ATRP method
Reinforcing agent.
The cyclodextrin is at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin.
The activated monomer containing double bonds is acryloyl chloride, methacrylic chloride, at least one in ethyl propylene acyl chlorides
Kind.
The acrylate monomers are sodium acrylate, Sodium methacrylate, ethylacrylic acid sodium, ammonium acrylate, methyl-prop
At least one of olefin(e) acid ammonium, ethylacrylic acid ammonium, potassium acrylate, methacrylic acid potassium, ethylacrylic acid potassium.
The acrylate monomer of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl
Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, methacrylate, ethylacrylic acid hydroxyl ethyl ester, ethylacrylic acid hydroxyl
At least one of propyl ester, ethylacrylic acid hydroxy butyl ester.
The ligand is N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ', N "-pentamethyl methyl acrylate base diethyl
Alkenyl triamine, N, N, N ', N ', N ", N "-hexamethyl n-butyl acrylate base triethylene tetraamine, 2,2 '-bipyridyls, N, N, N ',
N ', N "-pentamethyldivinyltriamine, N, N, N ', N ', N ", in N "-hexamethyl methyl acrylate base triethylene tetraamine extremely
Few one kind.
The catalyst is at least one of cuprous bromide, stannous chloride, copper bromide.
The surfactant is double dodecylphenyl ether sodium disulfonates, odium stearate, sodium laurate, OP-10, benzene second
Base phenol polyethenoxy ether, tween, fatty alcohol polyoxyethylene ether, octadecyldimethyl vinyl phenyl ammonium chloride, dodecyl two
At least one of ethylene methacrylic Phenyl chloride.
The initiator is 4- [2- (the bromo- 2- methylpropionyloxy of 2-) ethyoxyl] -4- oxo -2- sulfonic group butyric acid two
Sodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) decyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [6- (the bromo- 2- first of 2-
Base propionyloxy) hexyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) pungent oxygen
Base] -4- oxo -2- sulfonic group butyric acid disodium, N, at least one of N- diethyl -2- bromo acrylamide.
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, synthetic reaction formula are as follows:
Copolymer ceramic green body reinforcing agent action principle of the invention: when being not added with reinforcing agent between green body pulp particle
In conjunction with being by Van der Waals force, after reinforcing agent is added, the bonding mechanism of green body pulp particle depends on the structure of enhancing agent molecule；
Copolymer reinforcing agent of the present invention, the high molecular polymer with enough chain lengths, the hydroxyl more being distributed is conducive to and green body
Pulp particle forms Hydrogenbond, and the repetitive unit that copolymer segment is constituted from the cyclodextrin of special construction can be with different green bodies
Bridging action is played between particle, irregular reticular structure is formed and green body pulp particle is tightly wrapped up, and plays efficient humidification.
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method of the present invention, has following spy
Point: (1) for the first time using ATRP method preparation modified cyclodextrin copolymers ceramic green body reinforcing agent, narrow molecular weight distribution, PDI≤
1.3, performance is stablized；(2) the copolymer ceramic green body reinforcing agent is using cyclodextrin, hydroxy-acrylate monomer as repetitive unit,
With high hydroxyl content, strong hydrogen bonding effect can occur with green body pulp particle；Simultaneously because cyclodextrin has special peviform knot
Structure forms winding and cladding to green body pulp particle, therefore reinforcing effect is more efficient；(3) in the copolymer ceramics reinforcing agent
Acrylate monomers are introduced, there is good dispersibility, it is small to the viscosity influence of green body slurry, therefore use ceramics of the invention
Reinforcing agent is without additional addition degumming agent.
Specific embodiment
Below with reference to the embodiment cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method a kind of to the present invention
It is further described.It is understood that specific embodiment described herein is used only for explaining related invention, rather than it is right
The restriction of the invention.
Embodiment 1
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, preparation step are as follows:
A) 20.0 parts of alpha-cyclodextrins are dissolved in DMSO, 65 DEG C is heated under stirring, 1.9g ethyl propylene is added dropwise dropwise
Acyl chlorides is added dropwise in 0.5h, then the reaction was continued at 65 DEG C 13h, is cooled to room temperature, and methanol dilution is added, uses acetone
Precipitating, is obtained by filtration micro- light yellow solid, then with acetone washing 3 times, obtain the modified cyclodextrin monomer of light yellow solid；
B) successively by 30.0 parts of sodium acrylate, 15.0 parts of non-ionic monomers, 30.0 parts of modified cyclodextrin monomers, 1.0 parts of N,
N, N ', N ', N ", N "-hexamethyl methyl acrylate base triethylene tetraamine, 0.5 part of cuprous bromide, 0.3 part OP-10 and 100 part
Deionized water is added in reactor, is heated up 90 DEG C after stirring and dissolving, and 5.0 parts of 15% part of 4- [2- (bromo- 2- methyl-props of 2- are added dropwise
Acyloxy) ethyoxyl] two sodium water solution of -4- oxo -2- sulfonic group butyric acid, it is added dropwise in 1h, is then reacted at 70 DEG C
3h, cold filtration, filter cake is washed, dry, granulation, packs, and obtains the modified cyclodextrin copolymers ceramic body of the ATRP method
Reinforcing agent.
Performance test: according to the reinforcing effect of sanitary ceramics production practical methods measurement product: by Foshan ceramics
Company standard mud measures 500ml mud after mixing evenly, with the measuring cup of 1000ml, and copolymer described in embodiment 1 is added
Ceramic green body reinforcing agent 0.16g stirs 5min under high-speed mixer, is then poured into standard Triangle ID (side length 30mm) mold
And start to use manual time-keeping, mold is opened after 30min, operation temperature is room temperature, and initial cracking time 25min33s splits the time eventually
For 62min42s, length 15mm is split eventually；Do not add reinforcing agent mud under the same terms, initial cracking time 2min12s splits the time eventually
4min27s splits length 28mm eventually.
Embodiment 2
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, preparation step are as follows:
A) 20.0 parts of beta-cyclodextrins are dissolved in 40.0 parts of DMSO, 60 DEG C is heated under stirring, 2.4 part third is added dropwise dropwise
Alkene acyl chlorides, is added dropwise in 1h, then the reaction was continued at 60 DEG C 8h, is cooled to room temperature, and methanol dilution is added, heavy with acetone
It forms sediment, micro- light yellow solid is obtained by filtration, then with acetone washing 3 times, obtain the modified cyclodextrin monomer of light yellow solid；
B) successively by 40.0 parts of acrylate derivatives, 10.0 parts of Sodium methacrylates, 40.0 parts of modified cyclodextrin monomers,
0.1 part of 2,2 '-bipyridyl, 2.5 parts of stannous chlorides, 0.1 part of octadecyldimethyl vinyl phenyl ammonium chloride and 150.0 parts go from
Sub- water is added in reactor, is heated up 90 DEG C after stirring and dissolving, and 10.0 parts of 15% part of 4- [10- (bromo- 2- methyl propionyl of 2- are added dropwise
Oxygroup) decyloxy] two sodium water solution of -4- oxo -2- sulfonic group butyric acid, it is added dropwise in 0.5h, is then reacted at 90 DEG C
1h, cold filtration, filter cake is washed, dry, granulation, packs, and obtains the modified cyclodextrin copolymers ceramic body of the ATRP method
Reinforcing agent.
Performance test: according to the reinforcing effect of sanitary ceramics production practical methods measurement product: by Foshan ceramics
Company standard mud measures 500ml mud after mixing evenly, with the measuring cup of 1000ml, adds copolymer described in the present embodiment 2
Ceramic green body reinforcing agent 0.16g stirs 5min under high-speed mixer, is then poured into standard Triangle ID (side length 30mm) mold
And start to use manual time-keeping, mold is opened after 30min, operation temperature is room temperature, and initial cracking time 27min51s splits the time eventually
For 65min12s, length 14mm is split eventually；Do not add reinforcing agent mud under the same terms, initial cracking time 2min12s splits the time eventually
4min27s splits length 28mm eventually.
Embodiment 3
A kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, preparation step are as follows:
A) 20.0 parts of gamma-cyclodextrins are dissolved in 40.0 parts of DMSO, 70 DEG C is heated under stirring, 4.0 parts are added dropwise dropwise
Methacrylic chloride is added dropwise in 0.8h, then the reaction was continued at 70 DEG C 10h, is cooled to room temperature, and it is dilute that methanol is added
It releases, with acetone precipitation, micro- light yellow solid is obtained by filtration, then with acetone washing 3 times, obtain the modified cyclodextrin of light yellow solid
Monomer；
B) successively by 33.0 parts of acrylate derivatives, 12.0 parts of ammonium acrylates, 38.0 parts a) in modification containing double bonds
Cyclodextrin monomer, 0.3 part of N, N, N ', N ', N "-pentamethyldivinyltriamine, 2.0 parts of cuprous bromides, 0.2 part of dodecyl two
Ethylene methacrylic Phenyl chloride and 125.0 parts of deionized waters are added in reactor, are heated up 75 DEG C after stirring and dissolving, are added dropwise 8.0
15% part of two sodium water solution of 4- [6- (the bromo- 2- methylpropionyloxy of 2-) hexyloxy] -4- oxo -2- sulfonic group butyric acid of part,
It is added dropwise in 0.6h, 2h is then reacted at 76 DEG C, cold filtration, filter cake is washed, dry, granulation, packs, and obtains described
The modified cyclodextrin copolymers ceramic green body reinforcing agent of ATRP method.
Performance test: according to the reinforcing effect of sanitary ceramics production practical methods measurement product: by Foshan ceramics
Company standard mud measures 500ml mud after mixing evenly, with the measuring cup of 1000ml, adds copolymer described in the present embodiment 3
Ceramic green body reinforcing agent 0.16g stirs 5min under high-speed mixer, is then poured into standard Triangle ID (side length 30mm) mold
And start to use manual time-keeping, mold is opened after 30min, operation temperature is room temperature, and initial cracking time 24min24s splits the time eventually
For 60min31s, length 16mm is split eventually；Do not add reinforcing agent mud under the same terms, initial cracking time 2min12s splits the time eventually
4min27s splits length 28mm eventually.
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (9)
1. a kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method, it is characterised in that: the cyclodextrin is total
Polymers ceramic green body reinforcing agent, preparation step are as follows:
A) according to parts by weight, by 20.0 parts of cyclodextrins in 40.0 parts of DMSO, 60~70 DEG C are heated under stirring, dropwise
1.5~4.0 parts of activated monomers containing double bonds are added dropwise, are added dropwise in 0.5~1h, then the reaction was continued at 60~70 DEG C
8~13h, is cooled to room temperature, and methanol dilution is added, and with acetone precipitation, is obtained by filtration micro- light yellow solid, then with acetone washing 3
It is secondary, obtain the modified cyclodextrin monomer of light yellow solid；
B) successively by 30.0~40.0 parts of acrylate monomers, the acrylate monomer of 10.0~15.0 parts of hydroxyls, 30.0~
40.0 parts of modified cyclodextrin monomers, 0.1~1.0 part of ligand, 0.5~2.5 part of catalyst, 0.1~0.3 part of surfactant and
100.0~150.0 parts of deionized waters are added in reactor, and 60~90 DEG C are warming up to after stirring and dissolving, are added dropwise 5.0~10.0 parts
15% part of initiator solution, is added dropwise in 0.5~1h, and 1h~3h, cold filtration, filter are then reacted at 60~90 DEG C
Cake is washed, dry, granulation, packs, and obtains a kind of cyclodextrin copolymers ceramic green body reinforcing agent modified based on ATRP method；
The cyclodextrin copolymers ceramic green body reinforcing agent, molecular structural formula are as follows:
In structural formula, the R1、R2、R3For-H ,-CH3Or-CH2CH3；The M is Na+、K+Or NH4 +；The n=2~4, x=6
~10, y=5~10, z=15~30；Described its number-average molecular weight of cyclodextrin copolymers ceramic green body reinforcing agent be 15000~
25000, PDI≤1.3.
2. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the cyclodextrin is α-
At least one of cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin.
3. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: described containing double bonds
Activated monomer is at least one of acryloyl chloride, methacrylic chloride, ethyl propylene acyl chlorides.
4. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the acrylates
Monomer be sodium acrylate, Sodium methacrylate, ethylacrylic acid sodium, ammonium acrylate, ammonium methacrylate, ethylacrylic acid ammonium,
At least one of potassium acrylate, methacrylic acid potassium, ethylacrylic acid potassium.
5. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the third of the hydroxyl
Olefin(e) acid ester monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, metering system
Sour hydroxypropyl acrylate, methacrylate, ethylacrylic acid hydroxyl ethyl ester, ethylacrylic acid hydroxypropyl acrylate, ethylacrylic acid hydroxy butyl ester
At least one of.
6. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the ligand be N, N,
N ', N '-tetramethylethylenediamine, N, N, N ', N ', N "-pentamethyl methyl acrylate base diethylene triamine, N, N, N ', N ', N ",
N "-hexamethyl n-butyl acrylate base triethylene tetraamine, 2,2 '-bipyridyls, N, N, N ', N ', N "-pentamethyl divinyl three
Amine, N, N, N ', N ', N ", at least one of N "-hexamethyl methyl acrylate base triethylene tetraamine.
7. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the catalyst is bromine
Change at least one of cuprous, stannous chloride, copper bromide.
8. cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the surfactant
For double dodecylphenyl ether sodium disulfonates, odium stearate, sodium laurate, OP-10, phenethyl phenol polyethenoxy ether, tween, rouge
Fat alcohol polyoxyethylene ether, octadecyldimethyl vinyl phenyl ammonium chloride, in dodecyl dimethyl vinyl phenyl ammonium chloride
It is at least one.
9. a kind of cyclodextrin copolymers ceramic green body reinforcing agent according to claim 1, it is characterised in that: the initiation
Agent is 4- [2- (the bromo- 2- methylpropionyloxy of 2-) ethyoxyl] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (the bromo- 2- of 2-
Methylpropionyloxy) decyloxy] -4- oxo -2- sulfonic group butyric acid disodium, 4- [6- (the bromo- 2- methylpropionyloxy of 2-) own oxygen
Base] -4- oxo -2- sulfonic group butyric acid disodium, 4- [10- (the bromo- 2- methylpropionyloxy of 2-) octyloxy] -4- oxo -2- sulfonic acid
Base butyric acid disodium, N, at least one of N- diethyl -2- bromo acrylamide.
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| WO2024003339A1 (en) * | 2022-07-01 | 2024-01-04 | Lamberti Spa | Process for making tiles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101552A (en) * | 2017-12-26 | 2018-06-01 | 湖南辰砾新材料有限公司 | A kind of copolymer ceramic green body reinforcing agent and its ATRP the preparation methods based on cyclodextrin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101552A (en) * | 2017-12-26 | 2018-06-01 | 湖南辰砾新材料有限公司 | A kind of copolymer ceramic green body reinforcing agent and its ATRP the preparation methods based on cyclodextrin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024003339A1 (en) * | 2022-07-01 | 2024-01-04 | Lamberti Spa | Process for making tiles |
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Application publication date: 20190215 |