Background technology
Along with ceramic industry constantly uses high-quality china clay, cause the tonerde resource more and more deficienter, because it is non-renewable, ceramic industry is had to bring into use and is contained the more clay of poor material, be used for producing various ceramic products, yet because the congenital defect of material causes the ceramic body undercapacity, slurry is difficult to the problems such as dispergation, causes the product of producing that the defectives such as crackle, the angle of rupture, scarce limit are arranged.At present, what the China ceramic industry head it off generally adopted all is water reducer, and common ceramic water reducing agent is owing to be subjected to the impact of the factors such as molecular structure, relative molecular mass, and its effect is unsatisfactory, especially poor effect on blank strength and viscosity reduction.Affected high flowability and the mold effect that admittedly contains slurry.And the base substrate toughener domestic also mainly be to use methylcellulose gum, treated starch, polyvinyl alcohol etc., these organic high molecular polymer costs higher and also use also convenient not.Therefore, good height contains promotor admittedly can be issued at lower addition excellent effect, keeps good processing performance, promotes ceramic industry to less energy-consumption, high quality, the development of high yield aspect.
Ceramic industry is a high energy consumption industry, and wherein the energy more than 80% all is used to burn till and drying process.Day by day deep along with China's energy-saving and emission-reduction work, ceramic industry is faced with acid test, how energy-saving and emission-reduction become the major issue that current ceramics faces, and a guardian technique problem of energy-saving and emission-reduction is exactly how to reduce to obtain under the add-on of less water, and ceramic size still has preferably blank strength, flowability and lower viscosity.
What research was more at present is the polycarboxylic acid polymeric superplasticizer, and poly carboxylic acid just has high dispersing property and protects preferably the performance of collapsing through suitable modification under low incorporation.General all is to prepare first active large monomer, and then the monomer with certain proportioning mixes direct employing solution polymerization or obtains finished product through steps such as oversulfonate, esterifications.These methods, technique are comparatively complicated, and will introduce organic solvent, the technique such as need to remove after react again, separate complex, and not environmental protection, and market-oriented not, preparation cost is also higher.
And the adding of water reducer can not make blank strength increase, and is also not ideal enough for the ceramic size viscosity reduction dispersion effect that superelevation contains admittedly.
Therefore research admittedly contains ceramic size to height and has base substrate strengthens, viscosity reducing effect is good height and admittedly contain the promotor tool and have very important significance.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiency that above-mentioned prior art exists, and a kind of high ceramic size promotor that admittedly contains is provided, and can increase blank strength and viscosity reducing effect.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ceramic size height contains the preparation method of promotor admittedly, may further comprise the steps: 1) water, function monomer, first part's mineral-type chain-transfer agent are added mixing successively, stirring is warming up to 70-80 ℃ and gets the mixed solution I; 2) described mineral-type chain-transfer agent mix monomer and the water with unsaturated carboxylic acid class monomer and described function monomer and residue second section is mixed to get mix monomer, with the initiator initiator solution that is dissolved in water to get; 3) with step 2) the described mix monomer of gained and described initiator solution are parallel splashes into described step 1) in the described mixed solution I of gained, drip rear insulation 2-4h and get the mixed solution II; 4) with step 3) the described mixed solution II of gained is cooled to 40-50 ℃, and dripping mass concentration and be 30% sodium hydroxide solution to pH value is 6-8, drips cooling filtration blowing behind the rear insulation 0.5-1h, namely gets described ceramic size and admittedly contains promotor.
Admittedly contain among the preparation method of promotor at described ceramic size height, the consumption weight percent of described unsaturated carboxylic acid class monomer and function monomer is 20-35%, the consumption weight percent of described initiator is 0.2-1%, the consumption weight percent of described inorganic chain-transfer agent is 1-3%, the consumption weight percent of described sodium hydroxide is 10-20%, and the consumption weight percent of described aqueous solvent is 53-58%.
Admittedly contain among the preparation method of promotor at described ceramic size height, the consumption weight percent of described unsaturated carboxylic acid class monomer and function monomer is respectively 10-30% and 2-15%; The usage ratio of the described mineral-type chain-transfer agent of the described mineral-type chain-transfer agent of first part and second section is 3:7~5:5.
Admittedly contain among the preparation method of promotor at described ceramic size height, described unsaturated carboxylic acid class monomer is selected from least a in vinylformic acid, methacrylic acid, methylene-succinic acid and the fumaric acid.
Admittedly contain among the preparation method of promotor at described ceramic size height, described function monomer is selected from least a in maleic anhydride, acrylamide, methylpropene sodium sulfonate, sodium allyl sulfonate, N hydroxymethyl acrylamide and 2-acrylamido-2-methacrylic sulfonic acid.
Admittedly contain among the preparation method of promotor described step 1 at described ceramic size height) and step 2) used described function monomer be selected from respectively in maleic anhydride, acrylamide, methylpropene sodium sulfonate, sodium allyl sulfonate, N hydroxymethyl acrylamide and 2-acrylamido-2-methacrylic sulfonic acid each is a kind of.
Admittedly contain among the preparation method of promotor at described ceramic size height, described initiator is persulphate, initiator system of ammonium persulfate.
Admittedly contain in the promotor at described ceramic size height, described mineral-type chain-transfer agent is sodium bisulfite or inferior sodium phosphate.
A kind of ceramic size height contains promotor admittedly, is to obtain by preparation method described above.
Compared with prior art, the present invention has following beneficial effect: ceramic size of the present invention contains promotor admittedly, in the slurry drying process, can become immobilising gel to losing flowability from viscous state, becomes at last solid.And with base substrate after 110 ℃ of (admittedly containing the promotor decomposition temperature far below this) dryings, molecular structure still is the long-chain shape.And the molecule long-chain can be built bridge between ceramic particle, produces crosslinked action and forms irregular reticulated structure, and ceramic particle is tightly wrapped up, and plays the effect that fiber increases blank strength.Before base substrate fracture, put on a part of load on the base substrate by having stronger flexibility and the elastic promotor molecule long-chain that admittedly contains is shared, thereby can increase blank strength.This contains the viscosity reducing effect that promotor also has excellence admittedly simultaneously, forms layer protecting film on the pulp particle surface and can prevent particle aggregation, improves material fluidity, thereby improves grinding efficiency, shortens milling time.Therefore, the solid content of ceramic size is significantly promoted, the stability of slurry is strengthened, ceramic particle can keep relative stability and good dispersion state the long period, being convenient in moulding process ceramic particle can densification pile up, thereby can obtain having well behaved ceramic body.
Embodiment
In order to further specify principle of the present invention, existing to a preferred embodiment of the present invention will be described in detail.
Ceramic size height of the present invention contains the preparation method of promotor admittedly, may further comprise the steps: 1) water, function monomer, first part's mineral-type chain-transfer agent are added mixing successively, stirring is warming up to 70-80 ℃ and gets the mixed solution I; 2) described mineral-type chain-transfer agent mix monomer and the water with unsaturated carboxylic acid class monomer and described function monomer and residue second section is mixed to get mix monomer, with the initiator initiator solution that is dissolved in water to get; 3) with step 2) the described mix monomer of gained and described initiator solution are parallel splashes into described step 1) in the described mixed solution I of gained, drip rear insulation 2-4h and get the mixed solution II; 4) with step 3) the described mixed solution II of gained is cooled to 40-50 ℃, and dripping mass concentration and be 30% sodium hydroxide solution to pH value is 6-8, drips cooling filtration blowing behind the rear insulation 0.5-1h, namely gets described ceramic size and admittedly contains promotor.
Admittedly contain among the preparation method of promotor at described ceramic size height, the consumption weight percent of described unsaturated carboxylic acid class monomer and function monomer is 20-35%, the consumption weight percent of described initiator is 0.2-1%, the consumption weight percent of described inorganic chain-transfer agent is 1-3%, the consumption weight percent of described sodium hydroxide is 10-20%, and the consumption weight percent of described aqueous solvent is 53-58%.
Admittedly contain among the preparation method of promotor at described ceramic size height, the consumption weight percent of described unsaturated carboxylic acid class monomer and function monomer is respectively 10-30% and 2-15%; The usage ratio of the described mineral-type chain-transfer agent of the described mineral-type chain-transfer agent of first part and second section is 3:7~5:5.
Admittedly contain among the preparation method of promotor at described ceramic size height, described unsaturated carboxylic acid class monomer is selected from least a in vinylformic acid, methacrylic acid, methylene-succinic acid and the fumaric acid.
Admittedly contain among the preparation method of promotor at described ceramic size height, described function monomer is selected from least a in maleic anhydride, acrylamide, methylpropene sodium sulfonate, sodium allyl sulfonate, N hydroxymethyl acrylamide and 2-acrylamido-2-methacrylic sulfonic acid.
Admittedly contain among the preparation method of promotor described step 1 at described ceramic size height) and step 2) used described function monomer be selected from respectively in maleic anhydride, acrylamide, methylpropene sodium sulfonate, sodium allyl sulfonate, N hydroxymethyl acrylamide and 2-acrylamido-2-methacrylic sulfonic acid each is a kind of.
Admittedly contain among the preparation method of promotor at described ceramic size height, described initiator is persulphate, initiator system of ammonium persulfate.
Admittedly contain in the promotor at described ceramic size height, described mineral-type chain-transfer agent is sodium bisulfite or inferior sodium phosphate.
Below enumerate four embodiment, the present invention is further elaborated.
Example 1:1) in the four-hole boiling flask of 250ml, add 15g water, 6g methylpropene sodium sulfonate, 1.4g inferior sodium phosphate, the unlatching stirring and dissolving is warming up to 70 ℃ and gets the mixing solutions I; 2) 32g vinylformic acid, 5.2g acrylamide, 1g inferior sodium phosphate and 7g water are mixed to get mix monomer, the 0.7g ammonium persulphate are dissolved in get initiator solution in the 15g water; 3) with step 2) mix monomer of gained and initiator solution is parallel splashes in the step 1) gained mixing solutions I, 2.5h drips rear insulation 3h and gets the mixing solutions II; 4) the mixing solutions II is cooled to 45 ℃, regulates pH value to 7 with 30% sodium hydroxide solution; After having regulated, insulation 0.5h, cooling filtration blowing namely gets described ceramic size and admittedly contains promotor.
Example 2:1) in the four-hole bottle of 250ml, add 15g water, 5.6g maleic anhydride, 2.4g sodium bisulfite, the unlatching stirring and dissolving is warming up to 75 ℃ and gets the mixing solutions I; 2) 32g vinylformic acid, 4.8g 2-acrylamido-2-methacrylic sulfonic acid, 1.6g sodium bisulfite and 7g water are mixed to get mix monomer; The 0.7g ammonium persulphate is dissolved in the 15g water to get initiator solution; 3) with step 2) mix monomer of gained and initiator solution is parallel splashes in the step 1) gained mixing solutions I, 3h drips rear insulation 4h and gets the mixing solutions II; 4) the mixing solutions II is cooled to 40 ℃, regulates pH value to 6 with 30% sodium hydroxide solution; After having regulated, insulation 0.5h, cooling filtration blowing namely gets described ceramic size and admittedly contains promotor.
Example 3:1) in the four-hole bottle of 250ml, add 15g water, 5.6g sodium allyl sulfonate, 2g inferior sodium phosphate, open stirring and dissolving and be warming up to 80 ℃ of mixing solutions I; 2) 20g methacrylic acid, 18g methylene-succinic acid, 0.8g N hydroxymethyl acrylamide, 1g inferior sodium phosphate and 7g water are mixed to get mix monomer; The 0.8g ammonium persulphate is dissolved in the 15g water to get initiator solution; 3) with step 2) mix monomer of gained and initiator solution is parallel splashes in the step 1) gained mixing solutions I, 2-3h drips rear insulation 2h and gets the mixing solutions II; 4) the mixing solutions II is cooled to 50 ℃, regulates pH value to 8 with 30% sodium hydroxide solution; After having regulated, insulation 0.5-1h, cooling filtration blowing namely gets described ceramic size and admittedly contains promotor.
Example 4:1) in the four-hole boiling flask of 250ml, add 15g water, 6g maleic anhydride, 1.4g inferior sodium phosphate, the unlatching stirring and dissolving is warming up to 70 ℃ and gets the mixing solutions I; 2) 32g vinylformic acid, 2g acrylamide, 1g inferior sodium phosphate and 7g water are mixed to get mix monomer, the 0.7g ammonium persulphate are dissolved in get initiator solution in the 15g water; 3) with step 2) mix monomer of gained and initiator solution is parallel splashes in the step 1) gained mixing solutions I, 2.5h drips rear insulation insulation 3h and gets the mixing solutions II; 4) the mixing solutions II is cooled to 45 ℃, regulates pH value to 7 with 30% sodium hydroxide solution; After having regulated, insulation 0.5h, cooling filtration blowing namely gets described ceramic size and admittedly contains promotor.
Below be to adopt ceramic size of the present invention admittedly to contain the mensuration of ceramic body intensity after the promotor and the mensuration of ball milling effect.
1, the mensuration of ceramic body intensity: ceramic size of the present invention is contained promotor admittedly respectively by different add-ons and 50 mL water wiring solution-formings, then join in the blank with spray pattern, mix well, then cross 20 mesh sieves.The massfraction of water is 5 %~6 % in the control blank, and shelving 24 h then are again with the pressure semi-dry pressing of 18 MPa.After in 110 ℃ of baking ovens, drying, make the sample of 70mm * 30 mm * 7 mm, test intensity at tcs-1000 type Intensity of Breaking Tester, enhancing rate (%)=((add ceramic body intensity behind the toughener-do not add toughener ceramic body intensity)/do not add toughener ceramic body intensity) * 100.
Sequence number |
Sample |
Umber (oven-dry weight) |
Dry tenacity/MPa |
Enhancing rate % |
1 |
Blank |
0 |
1.428 |
? |
2 |
Example 1 |
0.2 |
2.102 |
47.20 |
3 |
Example 2 |
0.2 |
2.091 |
46.43 |
4 |
Example 3 |
0.2 |
2.087 |
46.15 |
5 |
Example 4 |
0.2 |
2.094 |
46.78 |
6 |
The market like product |
0.2 |
2.074 |
45.24 |
2, the mensuration of ball milling effect: mud viscosity and the mensuration that tails over: ceramic raw material silt particle mass ratio is 1:4; The feed ratio that drops into ball mill is: m (raw material): m (ball): m (water) is 4: 3: 1.55 and specified amount sample.Behind the ball milling 3h, measure the viscosity of mud with rotational viscosimeter, and ball milling mud is crossed 200 mesh sieves, mensuration tails over.
Add viscosity and 200 mesh screen residues of measuring mud behind the product of the present invention and the results are shown in following table:
Sequence number |
Sample |
Umber (oven-dry weight) |
Viscosity/MPa.s |
W (200 order) screen over-size % |
1 |
Blank |
0 |
690 |
? |
2 |
Example 1 |
0.1 |
180 |
0.4 |
3 |
Example 2 |
0.1 |
210 |
1.3 |
4 |
Example 3 |
0.1 |
250 |
1.5 |
5 |
Example 4 |
0.1 |
230 |
1.4 |
6 |
The market like product |
0.1 |
340 |
2.1 |
Can find out from above determination data, after in ceramic preparation technology, adopting ceramic size of the present invention admittedly to contain promotor, ceramic body intensity and ball milling effect are able to larger raising, its principle is as follows: ceramic size of the present invention contains promotor admittedly, in the slurry drying process, can become immobilising gel to losing flowability from viscous state, become at last solid.And with base substrate after 110 ℃ of (admittedly containing the promotor decomposition temperature far below this) dryings, molecular structure still is the long-chain shape.And the molecule long-chain can be built bridge between ceramic particle, produces crosslinked action and forms irregular reticulated structure, and ceramic particle is tightly wrapped up, and plays the effect that fiber increases blank strength.Before base substrate fracture, put on a part of load on the base substrate by having stronger flexibility and the elastic promotor molecule long-chain that admittedly contains is shared, thereby can increase blank strength.This contains the viscosity reducing effect that promotor also has excellence admittedly simultaneously, forms layer protecting film on the pulp particle surface and can prevent particle aggregation, improves material fluidity, thereby improves grinding efficiency, shortens milling time.Therefore, the solid content of ceramic size is significantly promoted, the stability of slurry is strengthened, ceramic particle can keep relative stability and good dispersion state the long period, being convenient in moulding process ceramic particle can densification pile up, thereby can obtain having well behaved ceramic body.
Summary is got up, and ceramic size of the present invention contains promotor admittedly, has following beneficial effect.
1. blank strength is improved a lot, having reduced ceramic product has the defectives such as crackle, the angle of rupture, scarce limit.
2. the ceramic size height admittedly contains promotor and can prevent effectively that slurry wadding is poly-, has preferably thermotolerance, weathering resistance, dispersiveness and water-reducing effect, has improved the ball milling speed of ceramic size, has reduced milling time.
3. than the viscosity that can effectively improve slurry under the low water content, make slurry have good flowability, slurry concentration is higher, and effect is more obvious.
4, in addition, synthesis technique of the present invention is simple, and cost is low, and environmental protection and energy saving need not introduce organic solvent, and is more convenient during use.
Below only be better possible embodiments of the present invention, and unrestricted protection scope of the present invention, the equivalent structure that all utilizations specification sheets of the present invention and accompanying drawing content have been done changes, and all is included in protection scope of the present invention.