CN104192857A - Ammonium sulfamate-modified kaolin and preparation method thereof - Google Patents
Ammonium sulfamate-modified kaolin and preparation method thereof Download PDFInfo
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- CN104192857A CN104192857A CN201410412589.6A CN201410412589A CN104192857A CN 104192857 A CN104192857 A CN 104192857A CN 201410412589 A CN201410412589 A CN 201410412589A CN 104192857 A CN104192857 A CN 104192857A
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- kaolin
- dmso
- kac
- ammonium sulfamate
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Abstract
The invention relates to ammonium sulfamate (AS) intercalated and modified kaolin and a preparation method of the ammonium sulfamate intercalated and modified kaolin. The method comprises the following steps: firstly, adding a proper amount of kaolin (K), dimethyl sulfoxide (DMSO) and distilled water to a three-necked flask, carrying out ultrasonic treatment for 5 hours in an ultrasonic reactor under the ultrasonic power of 100W; washing and drying, so as to obtain a kaolin-dimethyl sulfoxide (K-DMSO) compound; adding a proper amount of K-DMSO and a saturated potassium acetate (KAc) solution to the three-necked flask, stirring for 1d at 60 DEG C, washing and drying, so as to obtain a kaolin-potassium acetate (K-KAc) compound; and finally adding a proper amount of K-KAc and ammonium sulfamate solution to the three-necked flask, stirring for 1d at 60 DEG C, washing and drying, so as to obtain a kaolin-ammonium sulfamate (K-AS) compound. According to the method, the fire retardant containing N and S flame retardant elements is introduced between kaolin layers, so that the kaolin containing the N and S flame retardant elements is obtained, and the flame retardant property of the material can be improved.
Description
Technical field
The present invention relates to Ammonium sulfamate modified kaolin field, be specifically related to Ammonium sulfamate modified kaolin and preparation method
Background technology
Kaolin (Kaolinite, K) belongs to typical two-layer silicate sturcture, and its desirable chemical formula is Al
2[(OH)
4/ Si
2o
5], belong to triclinic(crystalline)system, be by SiO
4tetrahedral six side's stratum reticulare and AlO
2(OH)
4octahedra stratum reticulare is done periodic arrangement and the laminate structure in conjunction with formation by 1:1 on C axle.Make it in fields such as Industrial Catalysis, biological medicine, environment protection, electronic material, nano composite material, fire retardant materials, be applied widely and demonstrate good prospect.
In recent years, the application of stratified nano materials is more and more wider, as quite active in the applied research in the fields such as fire-retardant, catalysis and electrorheological fluid, wherein functional ion introduced to intercalation material and unique performance of preparation in the middle of stratified material lamella and be valued by the people gradually.Kaolin belongs to non-expansibility layered silicate, different from polynite, interlayer is without interchangeability ion, between tetrahedral si-o film and aluminum oxide octahedral sheet, depositing asymmetric effect, interlayer is mainly with hydrogen bonded, so kaolin interlayer adhesion force is large, so the intercalation between kaolin and organism is more difficult.Research shows, only have the strong polar micromolecules of minority can directly be intercalation under certain conditions kaolin interlayer, as dimethyl sulfoxide (DMSO), hydrazine, Potassium ethanoate and methane amide etc., other molecules, as pyridine, 1-2-propylene glycol, benzamide, polyvinylpyrrolidone and polymethylmethacrylate etc. all can not directly be intercalation into kaolin interlayer, but can by bioactive molecule carry secretly or metathesis enters interlayer, thereby indirectly realize kaolinic intercalation modifying.
In Ammonium sulfamate (AS), contain amino and sulfur-to-oxygen double bond, the method replacing by intercalation can make TU and kaolinic internal surface hydroxyl form hydrogen bond, thereby AS is incorporated into kaolin interlayer, and in TU, contains ignition-proof element N and S, can further improve the flame retardant properties of matrix.
Summary of the invention
The object of the invention is to be to prepare Ammonium sulfamate modified kaolin, the fire retardant containing N and S ignition-proof element is inserted into kaolin interlayer by ultrasonic and chemical reaction, improve kaolinic flame retardant properties comprehensively.
For achieving the above object, the present invention adopts following technical scheme:
First by 20 to 40 mass parts chemical formulas, be Al
2[(OH)
4/ Si
2o
5] kaolin (K), 200 to 400 mass parts dimethyl sulfoxide (DMSO) (DMSO) and 20 to 50 mass parts deionized waters join in there-necked flask, be put in ultrasound reactor, ultrasonic power 100W to 250W, ultrasonic time 2h to 8h, washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 to 2 mass parts K-DMSO and saturated acetic acid potassium (KAc) solution joins in there-necked flask, under 60 ℃ of conditions, react 1 to 3d, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 to 2 mass parts K-KA sample and 3mol/L to 8mol/L thionamic acid ammonium solution 20mL joins in there-necked flask, under 60 ℃ of conditions, react 1 to 3d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
The present invention has prepared a kind of brand-new interlayer modified kaolin, and the fire retardant Ammonium sulfamate containing N and S ignition-proof element is intercalation into kaolin interlayer, and technique is simple, raw material is easy to get, preparation amount is large, and transformation efficiency is high, can be used as a kind of novel high molecular fire retardant additive.
In practical application, modified kaolin prepared by the present invention can with the blend of various kinds of resin matrix, thereby the nano composite material of obtaining.Modified kaolin can well improve the flame retardant properties of matrix resin material.
Accompanying drawing explanation
Fig. 1 is modified kaolin and the original kaolinic FTIR comparison diagram that the embodiment of the present invention provides;
Fig. 2 is modified kaolin and the original kaolinic XRD comparison diagram that the embodiment of the present invention provides
Fig. 3 is the modified kaolin (K-AS) and original kaolinic TG comparison diagram that the embodiment of the present invention provides.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is carried out to comparatively detailed explanation.
Embodiment 1:
(1) 24 mass parts kaolin (K), 240ML dimethyl sulfoxide (DMSO) (DMSO) and 27ML deionized water are joined in there-necked flask, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 5h, and washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 mass parts K-DMSO and 20mL saturated acetic acid potassium (KAc) solution joins in there-necked flask, continuously stirring reaction 1d under 60 ℃ of conditions, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 mass parts K-KAc and 20mL8mol/L thionamic acid ammonium solution joins in there-necked flask, under 60 ℃ of conditions, react 1d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
Modified kaolin and kaolin are carried out to FTIR analysis, Comparatively speaking, after DMSO intercalation kaolin soil, 3694cm
-1the intensity at peak, place is with respect to 3621cm
-1place obviously declines, and illustrates that kaolinic a large amount of internal surface hydroxyl is destroyed, and original 3670 and 3653cm
-1the absorption peak at place is by 3663cm
-1the absorption peak at place replaces; 3022 and 2937cm
-1, there is methyl antisymmetric stretching vibration peak and symmetrical stretching vibration peak in place, and at 1319cm
-1having there is the flexural vibration peak of methyl in place, illustrates that DMSO may interaction occur with kaolin internal surface hydroxyl; From the spectrogram of K-KAc, find, at 3607cm
-1having there is new absorption peak in place, represents that the insertion kaolin of KAc has affected the hydrogen bond structure in K-DMSO, 1602 and 1420cm
-1place has occurred representing respectively COO by new absorption peak
-antisymmetric stretching vibration peak and symmetrical stretching vibration peak, illustrate that KAc replaces MeOH, there is interaction in KAc and kaolin internal surface hydroxyl; From the spectrogram of K-AS, find, at 3611cm
-1having there is new absorption peak in place, represents that the insertion kaolin of AS has affected the hydrogen bond structure in K-KAc, 1404,1258 and 1206cm
-1place has occurred representing respectively SOO by new absorption peak
-antisymmetric stretching vibration peak and symmetrical stretching vibration peak.
In order further to verify modified kaolin and kaolin to be carried out to XRD analysis.With DMSO, KAc and AS modification successively, kaolinic interlamellar spacing is corresponding there is movement, is embodied in d
001the variation of value, in kaolinic XRD spectra, kaolinic 001 crystal face appears at 2 θ=12.4 °.After DMSO modification, diffraction peak moves to 7.9 ° to low angle.When using KAc Modified K-DMSO, the diffraction peak of 001 crystal face of K-KAc moves to 6.2 °, and when using AS Modified K-KAc, the diffraction peak of 001 crystal face of K-AS moves 7.45 °, and intercalation rate reaches 90%.
Further checking, carries out thermogravimetic analysis (TGA) (TG) to kaolin and KDP modified kaolin again, can see mainly dehydroxylation between 500-600 ℃ of original high ridge, generates water; K-DMSO mainly removes the DMSO of interlayer, dehydroxylation between 500-600 ℃ between 120-180 ℃; K-KAc mainly removes the KAc of interlayer, dehydroxylation between 500-600 ℃ between 340-400 ℃; K-AS mainly removes the AS of interlayer between 200-400 ℃, dehydroxylation between 500-600 ℃, and after 600 ℃, carbon residue is further degraded.
Embodiment 2:
24 mass parts kaolin (K), 240ML dimethyl sulfoxide (DMSO) (DMSO) and 27ML deionized water are joined in there-necked flask, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 6h, and washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 mass parts K-DMSO and 20mL saturated acetic acid potassium (KAc) solution joins in there-necked flask, continuously stirring reaction 1d under 60 ℃ of conditions, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 mass parts K-KAc and 20mL8mol/L thionamic acid ammonium solution joins in there-necked flask, under 60 ℃ of conditions, react 1d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
Embodiment 3:
24 mass parts kaolin (K), 240ML dimethyl sulfoxide (DMSO) (DMSO) and 27ML deionized water are joined in there-necked flask, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 5h, and washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 mass parts K-DMSO and 20mL saturated acetic acid potassium (KAc) solution joins in there-necked flask, continuously stirring reaction 2d under 60 ℃ of conditions, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 mass parts K-KAc and 20mL8mol/L thionamic acid ammonium solution joins in there-necked flask, under 60 ℃ of conditions, react 1d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
Embodiment 4:
24 mass parts kaolin (K), 240ML dimethyl sulfoxide (DMSO) (DMSO) and 27ML deionized water are joined in there-necked flask, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 5h, and washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 mass parts K-DMSO and 20mL saturated acetic acid potassium (KAc) solution joins in there-necked flask, continuously stirring reaction 3d under 60 ℃ of conditions, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 mass parts K-KAc and 20mL8mol/L thionamic acid ammonium solution joins in there-necked flask, under 60 ℃ of conditions, react 1d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
Embodiment 5:
24 mass parts kaolin (K), 240ML dimethyl sulfoxide (DMSO) (DMSO) and 27ML deionized water are joined in there-necked flask, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 5h, and washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 mass parts K-DMSO and 20mL saturated acetic acid potassium (KAc) solution joins in there-necked flask, continuously stirring reaction 1d under 60 ℃ of conditions, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 mass parts K-KAc and 20mL3mol/L thionamic acid ammonium solution joins in there-necked flask, under 60 ℃ of conditions, react 1d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
Claims (6)
1. Ammonium sulfamate modified kaolin, is characterized in that: the fire retardant containing N and S ignition-proof element is intercalation into kaolin interlayer by ultrasonic and chemical reaction.
2. Ammonium sulfamate modified kaolin preparation method, its feature comprises the following steps: by 20 to 40 mass parts chemical formulas, be first Al
2[(OH)
4/ Si
2o
5] kaolin (K), 200 to 400 mass parts dimethyl sulfoxide (DMSO) (DMSO) and 20 to 50 mass parts deionized waters join in there-necked flask, be put in ultrasound reactor, ultrasonic power 100W to 250W, ultrasonic time 2h to 8h, washing is dried to obtain intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture; Then, get 1 to 2 mass parts K-DMSO and saturated acetic acid potassium (KAc) solution joins in there-necked flask, under 60 ℃ of conditions, react 1 to 3d, dry intercal type kaolin-Potassium ethanoate (K-KAc) mixture that to obtain of washing; Finally, get 1 to 2 mass parts K-KA sample and 3mol/L to 8mol/L thionamic acid ammonium solution 20mL joins in there-necked flask, under 60 ℃ of conditions, react 1 to 3d, dry intercal type kaolin-Ammonium sulfamate (K-AS) mixture that to obtain of washing.
3. Ammonium sulfamate modified kaolin preparation method according to claim 2, is characterized in that kaolin chemistry formula used is Al
2[(OH)
4/ Si
2o
5].
4. Ammonium sulfamate modified kaolin preparation method according to claim 2, it is characterized in that after the DMSO of 24 mass parts kaolin, 240 parts by volume and the mixing of 27 parts by volume deionized waters, be put in ultrasound reactor, ultrasonic power is 100W, ultrasonic time is 6h, with absolute ethanol washing 3 times, after 60 ℃ of freeze-day with constant temperature 12h intercal type kaolin-dimethyl sulfoxide (DMSO) (K-DMSO) mixture.
5. Ammonium sulfamate modified kaolin preparation method according to claim 2, it is characterized in that the saturated KAc solution of the K-DMSO of 1 mass parts and 20 parts by volume to join in beaker, under 60 ℃ of conditions, react 1d, with absolute ethanol washing 3 times, after 60 ℃ of freeze-day with constant temperature 12h intercal type kaolin-Potassium ethanoate (K-KAc) mixture.
6. Ammonium sulfamate modified kaolin preparation method according to claim 2, it is characterized in that the 8mol/L thionamic acid ammonium solution of the K-KAc of 1 mass parts and 20 parts by volume to join in there-necked flask, under 60 ℃ of conditions, react 1d, with absolute ethanol washing 3 times, after 60 ℃ of freeze-day with constant temperature 12h intercal type kaolin-Ammonium sulfamate (K-AS) mixture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130104A (en) * | 2017-12-28 | 2018-06-08 | 深圳市通产丽星股份有限公司 | A kind of Modification of kaolin grapheme material and preparation method thereof |
| CN108673705A (en) * | 2018-05-15 | 2018-10-19 | 王敏 | A kind of high-performance refractory plate and preparation method thereof |
| CN112853623A (en) * | 2021-01-07 | 2021-05-28 | 昆明理工大学 | Preparation method of electrospun kaolinite reinforced natural polysaccharide porous fiber membrane |
| CN113719313A (en) * | 2021-09-22 | 2021-11-30 | 重庆大学 | Modified kaolin gas coal dust composite explosion suppressant and preparation method thereof |
| CN117462432A (en) * | 2023-12-21 | 2024-01-30 | 铂臻(广州)生物科技有限公司 | Acne-removing composition and preparation method thereof |
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| CN103073012A (en) * | 2013-01-24 | 2013-05-01 | 中国高岭土有限公司 | Preparation method of superfine modified kaolin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130104A (en) * | 2017-12-28 | 2018-06-08 | 深圳市通产丽星股份有限公司 | A kind of Modification of kaolin grapheme material and preparation method thereof |
| CN108673705A (en) * | 2018-05-15 | 2018-10-19 | 王敏 | A kind of high-performance refractory plate and preparation method thereof |
| CN108673705B (en) * | 2018-05-15 | 2020-08-04 | 湖北巨江实业有限公司 | High-performance flame-retardant plate and preparation method thereof |
| CN112853623A (en) * | 2021-01-07 | 2021-05-28 | 昆明理工大学 | Preparation method of electrospun kaolinite reinforced natural polysaccharide porous fiber membrane |
| CN112853623B (en) * | 2021-01-07 | 2023-08-25 | 昆明理工大学 | Preparation method of electrostatic spinning kaolinite reinforced natural polysaccharide porous fiber membrane |
| CN113719313A (en) * | 2021-09-22 | 2021-11-30 | 重庆大学 | Modified kaolin gas coal dust composite explosion suppressant and preparation method thereof |
| CN117462432A (en) * | 2023-12-21 | 2024-01-30 | 铂臻(广州)生物科技有限公司 | Acne-removing composition and preparation method thereof |
| CN117462432B (en) * | 2023-12-21 | 2024-04-02 | 铂臻(广州)生物科技有限公司 | Acne-removing composition and preparation method thereof |
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Application publication date: 20141210 |