CN102675929A - Preparation method of fluorescent composite whitened attapulgite - Google Patents
Preparation method of fluorescent composite whitened attapulgite Download PDFInfo
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- CN102675929A CN102675929A CN2012101120887A CN201210112088A CN102675929A CN 102675929 A CN102675929 A CN 102675929A CN 2012101120887 A CN2012101120887 A CN 2012101120887A CN 201210112088 A CN201210112088 A CN 201210112088A CN 102675929 A CN102675929 A CN 102675929A
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- attapulgite
- recessed soil
- recessed
- coupling agent
- whitening
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Abstract
The invention discloses a preparation method of fluorescent composite whitened attapulgite, which is characterized by comprising the following steps: (1) after pulverizing attapulgite, screening, adding water to prepare a disperse system with a certain concentration, stirring, standing for some time, taking the supernatant suspension, carrying out centrifugal dewatering on the supernatant suspension, and drying at certain temperature to obtain purified attapulgite; (2) preparing the purified attapulgite into a dispersion, dropwisely adding a silane coupling agent while stirring, heating to react for some time, filtering, washing, drying, grinding and screening to obtain modified attapulgite; and (3) carrying out composite reaction on the modified attapulgite with a melamine-formaldehyde polycondensate and a water-soluble fluorescent whitening agent VBL to obtain the fluorescent whitened attapulgite. The attapulgite surface is modified by the silane coupling agent, thereby enhancing the dispersity of the attapulgite and the coupling action with resin; and the compound obtained by reacting the melamine-formaldehyde resin with the fluorescent whitening agent is compounded onto the attapulgite surface under the coupling action, thereby effectively enhancing the fixation action of the fluorescent whitening agent on the attapulgite surface and achieving the effect of whitening the attapulgite.
Description
Technical field
The present invention relates to the method for the recessed soil of a kind of fluorescence composite whitening, be specifically related to the method that recessed soil is brightened on a kind of surface that white dyes and polymkeric substance are compound to modified attapulgite.
Background technology
Recessed soil is a kind of widely used natural nonmetallic minerals, presents certain color and luster owing to containing certain impurity, and the recessed soil after the purification is white, in fields such as daily use chemicals, Polymer Synthesizing, papermaking, paint, has obtained using widely.The whiteness that improves recessed soil will help improving the added value that recessed soil is used, and enlarge the range of application of recessed soil in high-quality product.
In the fluorescent brightening of inorganic substance; Usually take direct stirring means to add anionic optical brighteners; Through adsorption anionic optical brighteners is attached to the inorganic substance surface and forms mixture; Inorganics generally is difficult for reaching the ideal whitening effect, and simple mixing and absorption can not let whitening agent and inorganics be evenly distributed each other, and especially to receive the influence of caly structure and surface property bigger for the application in clay class inorganic mineral.
In order to reach the purpose that effectively brightens of recessed soil, white dyes and polymkeric substance effectively are fixed to recessed soil surface, the intensity of strengthening white dyes should be the key of dealing with problems.
Recessed native surface is wetting ability, is suitable for using in the polar system.But in nonpolar organism and polymkeric substance, then be difficult to disperse.For this reason, need organically-modified (nonmetalliferous ore, 2007,30 (6): 1 ~ 4) are carried out in its surface.
One Chinese patent application (publication number CN 1882626A) discloses a kind of preparation method of fluorescent whiteninig pigments, and melamine-formaldehyde condensation polymer product and white dyes are obtained pigments for whitening, excellent performance in paper technology through polyreaction.
Summary of the invention
The objective of the invention is to: the method for the recessed soil of a kind of fluorescence composite whitening is provided, utilizes the method for chemically modified that recessed soil is carried out composite whitening, improve the added value of recessed soil.
Technical solution of the present invention is that this method of whitening may further comprise the steps: (1) is pulverized the back with recessed soil and is crossed 200 mesh sieves; Add water and be made into certain density dispersion system, stir, leave standstill for some time, get upper strata suspension-s centrifuge dehydration; In the certain temperature oven dry, recessed soil obtains purifying; (2) the recessed soil of will purifying is made into dispersion liquid, drips coupling agent in the stirring, and reacting by heating for some time, and the acquisition modified attapulgite filters, washs, dries, grinds, sieves; (3) modified attapulgite and melamine-formaldehyde condensation products and water soluble fluorescence whitening agent complex reaction make and brighten recessed soil.
Wherein, the concrete steps of this method of whitening are following:
(1) recessed soil is purified: choose recessed soil, cross 200 mesh sieves after crushed, adding water, to be made into mass concentration be 6% dispersion system; Stirred 1 hour, left standstill 6 hours, get upper strata suspension-s centrifuge dehydration; At 200 ~ 400 ℃ of oven dry recessed soil that obtains purifying, the whiteness of the recessed soil of purifying is more than 75.0%;
(2) recessed land reform property: the recessed soil of will purifying is made into the dispersion liquid that content is 50g/L ~ 100g/L; Drip the coupling agent of doing recessed soil property amount 5% ~ 10% while stirring; Be heated to 60 ℃ ~ 80 ℃ reactions 3 ~ 5 hours; Filter, the intact coupling agent of 6 flush away unreacteds of washing, 60 ℃ ~ 80 ℃ dryings are 3 ~ 5 hours in baking oven, grind 325 mesh sieves and obtain coupling agent modified recessed soil;
(3) complex reaction: to content is to add the white dyes of its quality 3 ~ 8% in penta hydroxy group-trimeric cyanamide of 60%, and adds water and stir to white dyes and all dissolve, and regulates pH value 3.5 ~ 4.5 with concentrated hydrochloric acid; The modified attapulgite that adds said mixture amount 50 ~ 70% stirs, and is heated to 70 ~ 90 ℃, and continuing with the salt acid for adjusting pH value is 1.5 ~ 2.5; 70 ~ 90 ℃ of stirring reactions 4 ~ 5 hours, behind the cool to room temperature, regulate pH value 9.0 ~ 10.0 with sodium hydroxide and alkalize; And carried out ball milling 1 ~ 2 hour; 325 mesh sieves were ground 60 ~ 80 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.
Wherein, coupling agent is an amino silicane coupling agent.
Beneficial effect of the present invention is:
1, the surperficial modification of recessed soil through silane coupling agent; Improved recessed soil dispersiveness and with the coupled action of resin; Melamine formaldehyde resin and white dyes reaction gained complex body are compound in recessed soil surface through coupled action; Thereby effectively improved the fixed action of white dyes, reached the effect that recessed soil brightens in recessed soil surface.
2, utilize cheap recessed soil resource, brighten recessed soil, improved the added value that recessed soil resource utilizes through the preparation of fluorescence composite methods.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.These embodiment can not be interpreted as it is the restriction to technical solution.
Embodiment 1
(1) recessed soil is purified: get recessed soil, cross 200 mesh sieves after crushed, adding water, to be made into mass concentration be 6% dispersion system, stirred 1 hour, left standstill 6 hours, gets upper strata suspension-s centrifuge dehydration, and at 200 ℃ of oven dry recessed soil that obtains purifying, whiteness is 75.0%;
(2) recessed land reform property: get in the recessed native 30g adding 500mL deionized water of purifying and join dispersion liquid; Drip the 3g silane resin acceptor kh-550 while stirring; Be heated to 80 ℃ of reactions 4 hours; Filter, the intact coupling agent of 6 flush away unreacteds of washing, 70 ℃ of dryings are 4 hours in baking oven, grind 325 mesh sieves and get coupling agent modified recessed soil;
(3) complex reaction: get the penta hydroxy group of 30g content 60%-trimeric cyanamide and add the 0.9g fluorescent whitening agent VBL, and add 100mL water and stir to white dyes and all dissolve, regulate pH value 4.0 with concentrated hydrochloric acid; Add the 21g modified attapulgite simultaneously and stir, be heated to 70 ℃, continuing with the salt acid for adjusting pH value is 2.0; 70 ℃ of stirring reactions 5 hours behind the cool to room temperature, are regulated pH value to 9 with sodium hydroxide solution and are alkalized; And carried out ball milling 1.5 hours; 325 mesh sieves were ground 70 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.Whiteness 88.7%.
Embodiment 2
(1) recessed soil is purified: get recessed soil, cross 200 mesh sieves after crushed, adding water, to be made into mass concentration be 6% dispersion system, stirred 1 hour, left standstill 6 hours, gets upper strata suspension-s centrifuge dehydration, and at 300 ℃ of oven dry recessed soil that obtains purifying, whiteness is 78.0%;
(2) recessed land reform property: get in the recessed native 30g adding 500mL deionized water of purifying and join dispersion liquid; Drip the 1.5g silane resin acceptor kh-550 while stirring; Be heated to 60 ℃ of reactions 5 hours; Filter, the intact coupling agent of 6 flush away unreacteds of washing, 80 ℃ of dryings are 3 hours in baking oven, grind 325 mesh sieves and get coupling agent modified recessed soil;
(3) complex reaction: get the penta hydroxy group of 30g content 60%-trimeric cyanamide and add the 1.8g fluorescent whitening agent VBL, and add 100mL water and stir to white dyes and all dissolve, regulate pH value 3.5 with concentrated hydrochloric acid; Add the 16g modified attapulgite simultaneously and stir, be heated to 80 ℃, continuing with the salt acid for adjusting pH value is 2.5; 80 ℃ of stirring reactions 4 hours behind the cool to room temperature, are regulated pH value to 10.0 with sodium hydroxide solution and are alkalized; And carried out ball milling 1 hour; 325 mesh sieves were ground 60 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.Whiteness 92.5%.
Embodiment 3
(1) recessed soil is purified: get recessed soil, cross 200 mesh sieves after crushed, adding water, to be made into mass concentration be 6% dispersion system, stirred 1 hour, left standstill 6 hours, gets upper strata suspension-s centrifuge dehydration, and at 400 ℃ of oven dry recessed soil that obtains purifying, whiteness is 80.0%;
(2) recessed land reform property: get in the recessed native 30g adding 500mL deionized water of purifying and join dispersion liquid; Drip the 2.3g silane resin acceptor kh-550 while stirring; Be heated to 70 ℃ of reactions 3 hours; Filter, the intact coupling agent of 6 flush away unreacteds of washing, 60 ℃ of dryings are 5 hours in baking oven, grind 325 mesh sieves and get coupling agent modified recessed soil;
(3) complex reaction: get the penta hydroxy group of 30g content 60%-trimeric cyanamide and add the 2.0g fluorescent whitening agent VBL, and add 100mL water and stir to white dyes and all dissolve, regulate pH value 4.5 with concentrated hydrochloric acid; Add the 16g modified attapulgite simultaneously and stir, be heated to 90 ℃, continuing with the salt acid for adjusting pH value is 1.5; 90 ℃ of stirring reactions 4.5 hours behind the cool to room temperature, are regulated pH value to 10.0 with sodium hydroxide solution and are alkalized; And carried out ball milling 2 hours; 325 mesh sieves were ground 80 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.Whiteness 93.9%.
Embodiment 4
(1) recessed soil is purified: with embodiment 3;
(2) recessed land reform property: get in the recessed native 30g adding 500mL deionized water of purifying and join dispersion liquid, drip 3g silane coupling agent KH-792 while stirring, all the other steps are with embodiment 1;
(3) complex reaction: get the penta hydroxy group of 30g content 60%-trimeric cyanamide and add the 2.4g fluorescent whitening agent VBL, and add 100mL water and stir to white dyes and all dissolve, regulate pH value 4.1 with concentrated hydrochloric acid; Add the 16g modified attapulgite simultaneously and stir, be heated to 75 ℃, continuing with the salt acid for adjusting pH value is 2.2; 75 ℃ of stirring reactions 5 hours behind the cool to room temperature, are regulated pH value to 9 with sodium hydroxide solution and are alkalized; And carried out ball milling 1.5 hours; 325 mesh sieves were ground 75 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.Whiteness 96.2%.
Claims (3)
1. the method for the recessed soil of fluorescence composite whitening; It is characterized in that this method of whitening may further comprise the steps: (1) is made into certain density dispersion system with recessed native grinding and sieving, Jia Shui, stirs, leaves standstill for some time, gets upper strata suspension-s centrifuge dehydration; Dry the recessed soil of to purify again under the certain temperature; (2) the recessed soil of will purifying is made into dispersion liquid, drips silane coupling agent in the stirring, reacting by heating for some time, filter, wash, dry, grind, sieve modified attapulgite; (3) modified attapulgite and melamine-formaldehyde condensation products and water soluble fluorescence whitening agent VBL complex reaction get the recessed soil of fluorescent brightening.
2. chemical modification method according to claim 1 brightens the method for recessed soil, it is characterized in that the concrete steps of this method of whitening are following:
(1) recessed soil is purified: choose recessed soil, cross 200 mesh sieves after crushed, adding water, to be made into mass concentration be 6% dispersion system; Stirred 1 hour, left standstill 6 hours, get upper strata suspension-s centrifuge dehydration; 200 ~ 400 ℃ of oven dry recessed soil that obtains purifying again, the whiteness of the recessed soil of purifying is more than 75%;
(2) recessed land reform property: the recessed soil of will purifying is made into the dispersion liquid that content is 50g/L ~ 100g/L; Drip the coupling agent of doing recessed soil property amount 5% ~ 10% while stirring; Be heated to 60 ℃ ~ 80 ℃ reactions 3 ~ 5 hours; Filter, the intact coupling agent of 5 ~ 7 flush away unreacteds of washing, 50 ℃ ~ 80 ℃ dryings are 3 ~ 5 hours in baking oven, grind 325 mesh sieves and obtain coupling agent modified recessed soil;
(3) complex reaction: to content is to add the white dyes of its quality 3 ~ 8% in penta hydroxy group-trimeric cyanamide of 60%, and adds water and stir to white dyes and all dissolve, and regulates pH value 3.5 ~ 4.5 with concentrated hydrochloric acid; The modified attapulgite that adds said mixture amount 50 ~ 70% stirs, and is heated to 60 ~ 90 ℃, continues to add hydrochloric acid and regulates acidity pH value 1.5 ~ 2.5; 60 ~ 90 ℃ of stirring reactions 4 ~ 5 hours, behind the cool to room temperature, regulate pH value 9.0 ~ 10.0 with sodium hydroxide and alkalize; And carried out ball milling 1 ~ 2 hour; 325 mesh sieves were ground 60 ~ 80 ℃ of vacuum-dryings in centrifugal washing back, got the recessed soil of fluorescence composite whitening.
3. chemical modification method according to claim 1 and 2 brightens the method for recessed soil, it is characterized in that: said silane coupling agent is an amino silicane coupling agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101120887A CN102675929B (en) | 2012-04-17 | 2012-04-17 | Preparation method of fluorescent composite whitened attapulgite |
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| CN2012101120887A CN102675929B (en) | 2012-04-17 | 2012-04-17 | Preparation method of fluorescent composite whitened attapulgite |
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Granted publication date: 20131204 Termination date: 20140417 |