CN103773082A - Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler - Google Patents
Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler Download PDFInfo
- Publication number
- CN103773082A CN103773082A CN201410052412.XA CN201410052412A CN103773082A CN 103773082 A CN103773082 A CN 103773082A CN 201410052412 A CN201410052412 A CN 201410052412A CN 103773082 A CN103773082 A CN 103773082A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- magnesium
- hydroxide
- flame retardant
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler. The preparation method comprises the following steps: adding water to calcium carbonate powder and magnesium sulfate so as to prepare slurry, adding calcium hydroxide to the slurry at a certain temperature, stirring, reacting for a certain time, then filtering, washing, drying, depolymerizing, and carrying out surface modification, thus obtaining the magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler. The inorganic composite flame retardant filler prepared by using the method has the excellent flame retardant property and smoke suppression property of magnesium hydroxide, also has the excellent filling technological property of calcium carbonate and the enhanced mechanical property and auxiliary flame retardant and smoke abatement property of calcium sulphate dehydrate, integrates multiple functions of filling enhancement, flame retardancy, smoke abatement and the like; the production cost of a magnesium hydroxide flame retardant is reduced, the functions of the calcium carbonate filler are added; and the magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler has good application prospect.
Description
Technical field
The preparation method who the present invention relates to a kind of magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler, belongs to inorganic fire-retarded filler technical field.
Background technology
Calcium carbonate powder material including heavy or fine grinding calcium carbonate and lightweight or precipitated chalk is because raw material sources are wide, handling ease, whiteness or brightness is high, color and luster is good, and the advantage such as low price, be the widest, the maximum inorganic mineral filler of consumption of the macromolecular material industry purposes such as current plastics, rubber, sizing agent, cable insulating material.But, although pearl filler has the function of difficult combustion, there is no fire-retardant function.Therefore, require more and more higher society in material safe handling, urgently wish that calcium carbonate can have certain anti-flaming function, the life and property loss causing to reduce fire as a kind of inorganic nonmetal mineral fillers being most widely used reducing macromolecular material cost and improve on the basis of material hardness and mechanical property.
Magnesium hydroxide has good flame retarding and smoke suppressing properties, and, when decomposes, discharge water outlet, absorb a large amount of latent heat simultaneously, reduce resin actual temperature of bearing in flame, have and suppress the cooling effect that superpolymer decomposes and inflammable gas produces, decomposing the magnesium oxide producing after moisture is good fire-resistant and porous material, can improve the ability of resin opposing flame and absorb flue dust, produce, use and discarded process in all unharmful substance discharges, be a kind of environment-friendly and green fire retardant.But the production cost of the high purity magnesium hydrate that chemical method is produced is higher, and in production process, produce a large amount of brine wastes to be processed that need, environment is caused to certain pressure; In addition, the fire-retardant oil-absorption(number) with super fine magnesium hydroxide is higher, is difficult in resin dispersedly while use separately, causes Drawing abillity variation.
The present invention is directed to the preparation method that above background proposes a kind of magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler.
Summary of the invention
Technical scheme of the present invention is, calcium carbonate powder and magnesium sulfate are added water after making slurries and adds at a certain temperature calcium hydroxide to carry out stirring reaction, stir while adding, after question response certain hour to product filter, wash, be dried, depolymerization and surface modification.
Its processing step is as follows:
(1) slurries preparation: calcium carbonate powder, magnesium sulfate are added water and stirred, make the suspension of favorable dispersity, the quality proportioning of magnesium sulfate, calcium carbonate powder and water is magnesium sulfate: calcium carbonate powder: water=100:150～350:300～700;
(2) Paris white surface clad magnesium hydroxide: add calcium hydroxide or dry hydrate in the slurries of preparing in step (1), stir, reaction generation magnesium hydroxide particles is coated on the composite particles on calcium carbonate granule surface, the addition of calcium hydroxide is 60%～80% of magnesium sulfate quality, coating reaction time 0.5h～3h, temperature of reaction is 50～95 ℃;
(3) reaction product filtered, carry out organic surface modifying after washing, dry, depolymerization.
Calcium carbonate powder described in technical solution of the present invention comprises take natural magnesium rocks such as calcite, marble, chalks as raw material, adopts the water-ground limestone of mechanical disintegration or Ginding process production and the light calcium carbonate that adopts calcining-digestion-removal of impurities-carbonization technique to produce take Wingdale as raw material; The fineness D of calcium carbonate
97=2～45 μ m(i.e. 325～5000 orders).
Technical solution of the present invention is as follows in the principle of carbonic acid particle surface coating reaction magnesium hydroxide:
MgSO
4+Ca(OH)
2+nH
2O→Mg(OH)
2+CaSO
4·2H
2O+(n-2)H
2O
Proportioning by calcium carbonate and magnesium sulfate in control calcium hydroxide interpolation speed, temperature of reaction, reaction times and slurries regulates and controls coated quality and the grain size of magnesium hydroxide on calcium carbonate granule surface, to meet the requirement in different application field.
The CaSO that reaction generates
42H
2o small part is dissolved in reaction solution and enters filtrate after filtration, after most of dry depolymerization, form microwhisker shape terra alba (gypsum), add the tensile strength that can strengthen composite flame-proof filler filled high polymer material in resin to, simultaneously due at 180 ℃ of left and right CaSO
42H
2o starts dehydration, therefore, also has and reduces the material surface temperature of catching fire, and stops the function of burning, and after dehydration, generates CaSO4(anhydrite) can also adsorb the flue dust that burning produces, reduce smoke density.
Being dried described in technical solution of the present invention, its drying temperature is less than 180 ℃.
After dry, depolymerization described in technical solution of the present invention, carry out organic surface modifying, properties-correcting agent is silane, stearic acid (salt) and combination thereof, and properties-correcting agent consumption is 1%～4% of composite flame-proof packing quality.
The inorganic compounding fire-retardant filler of preparing by the inventive method, both there is the good flame retardant properties of magnesium hydroxide, smoke suppressing, there is again enhancing mechanical property and assisting flame-resistant and the smoke elimination performance of the good fill process performance of calcium carbonate and terra alba, have concurrently to fill and strengthen and the several functions such as fire-retardant, smoke elimination; And, both reduced the production cost of flame retardant of magnesium hydroxide, increase again the function of pearl filler, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment mono-:
Get 200g magnesium sulfate and put into stirred reactor, add wherein 1000ml water, configuration Adlerika; In Adlerika, add water-ground limestone (D
97m) 400g of=5 μ, after stirring, makes mixed serum; Mixed serum is slowly added while stirring to calcium hydroxide 130g at 90 ℃ of constant temperature; After stirring reaction 150min, reaction product is filtered, washs, is dried, depolymerization, then carries out dry method modification with 10g silane and 5g stearic acid to it, obtains magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler.
Embodiment bis-:
Get 200g magnesium sulfate and put into stirred reactor, add wherein 1300ml water, configuration Adlerika adds water-ground limestone (D in Adlerika
97m) 600g of=10 μ, after stirring, makes mixed serum; Mixed serum is slowly added while stirring to calcium hydroxide 140g at 75 ℃ of constant temperature, after stirring reaction 120min, reaction product is filtered, washs, is dried, depolymerization, then with 11g silane and 6g stearic acid, it is carried out to dry method modification, obtain magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler.
Embodiment tri-:
Get 200g magnesium sulfate and put into stirred reactor, add wherein 1200ml water, configuration Adlerika adds light calcium carbonate (D in Adlerika
97m) 500g of=15 μ, after stirring, makes mixed serum; Mixed serum is slowly added while stirring to calcium hydroxide 130g at 70 ℃ of constant temperature, after stirring reaction 90min, reaction product is filtered, washs, is dried, depolymerization, then with 10g silane and 5g stearic acid, it is carried out to dry method modification, obtain magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler.
Embodiment tetra-:
Get 200g magnesium sulfate and put into stirred reactor, add wherein 1300ml water, configuration Adlerika adds light calcium carbonate (D in Adlerika
97m) 600g of=30 μ, after stirring, makes mixed serum; Mixed serum is slowly added while stirring to calcium hydroxide 140g at 70 ℃ of constant temperature, after stirring reaction 120min, reaction product is filtered, washs, is dried, depolymerization, then with 12g silane and 6g stearic acid, it is carried out to dry method modification, obtain magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler.
Table 1 magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler performance
Claims (3)
1. a preparation method for magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler, is characterized in that its processing step is:
(1) slurries preparation: calcium carbonate powder, magnesium sulfate are added water and stirred, make dispersion suspension liquid, the quality proportioning of magnesium sulfate, calcium carbonate powder and water is magnesium sulfate: calcium carbonate powder: water=100:150～350:250～700;
(2) calcium carbonate surface clad magnesium hydroxide: add calcium hydroxide or dry hydrate to carry out stirring reaction in the slurries of preparing in step (1), generate the composite particles that magnesium hydroxide particles is coated on calcium carbonate granule surface, the addition of calcium hydroxide is 60%～80% of magnesium sulfate quality, coating reaction time 0.5h～3h, temperature of reaction is 50～95 ℃;
(3) reaction product filtered, carry out organic surface modifying after washing, dry, depolymerization.
2. the preparation method of a kind of magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler according to claim 1, it is characterized in that described calcium carbonate powder comprises take natural magnesium rocks such as calcite, marble, chalks as raw material, adopt the water-ground limestone of mechanical disintegration or Ginding process production and the light calcium carbonate that adopts calcining-digestion-removal of impurities-carbonization technique to produce take Wingdale as raw material; The fineness D of calcium carbonate
97=2～45 μ m(i.e. 325～5000 orders).
3. the preparation method of a kind of magnesium hydroxide coated caco3 inorganic compounding fire-retardant filler according to claim 1, it is characterized in that described organic surface modifying, properties-correcting agent is silane, stearic acid (salt) and combination thereof, and properties-correcting agent consumption is 1%～4% of composite flame-proof packing quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052412.XA CN103773082B (en) | 2014-02-17 | 2014-02-17 | Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052412.XA CN103773082B (en) | 2014-02-17 | 2014-02-17 | Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103773082A true CN103773082A (en) | 2014-05-07 |
| CN103773082B CN103773082B (en) | 2015-04-01 |
Family
ID=50565869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410052412.XA Active CN103773082B (en) | 2014-02-17 | 2014-02-17 | Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103773082B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059392A (en) * | 2014-05-27 | 2014-09-24 | 池州凯尔特纳米科技有限公司 | Porous material modified calcium carbonate and preparation method thereof |
| CN104387615A (en) * | 2014-12-08 | 2015-03-04 | 太原理工大学 | Preparation method of magnesium hydroxide-coated talcum powder composite flame-retardant filler |
| CN104403372A (en) * | 2014-12-08 | 2015-03-11 | 广西利升石业有限公司 | Dry-process preparation method of superfine heavy calcium carbonate |
| CN104892980A (en) * | 2015-06-05 | 2015-09-09 | 葫芦岛首创科技有限公司 | Preparation method of nano-CaCO3-coated brucite composite material |
| CN106221291A (en) * | 2016-07-13 | 2016-12-14 | 凤台县泓瀚建筑防水材料厂 | The span of a kind of magnesium hydroxide cladding carrys out polyimide modified pearl filler |
| CN106395877A (en) * | 2016-08-30 | 2017-02-15 | 青岛食安生物工程有限公司 | Preparation process of pure natural nano-ultrafine calcium powders |
| CN109879302A (en) * | 2019-04-01 | 2019-06-14 | 东北大学 | Magnesium hydroxide/expansible graphite composite material method is prepared by raw material of magnesium carbonate mine |
| CN110606500A (en) * | 2019-10-17 | 2019-12-24 | 四川新莱特新型建材有限公司 | Production process of calcium carbonate-magnesium oxide composite nano material |
| CN111048261A (en) * | 2019-10-21 | 2020-04-21 | 东莞福川精密工业股份有限公司 | Anti-aging flame-retardant cable and processing technology |
| CN113845717A (en) * | 2021-11-16 | 2021-12-28 | 苏州亨利通信材料有限公司 | Low-cost waterproof low-smoke halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
| CN113861664A (en) * | 2021-10-20 | 2021-12-31 | 荣威达光电(东莞)有限公司 | Wear-resistant flame-retardant TPU material and preparation method thereof |
| CN116514457A (en) * | 2023-05-23 | 2023-08-01 | 四川公路桥梁建设集团有限公司 | Flame-retardant asphalt mixture and preparation method thereof |
| CN116731397A (en) * | 2023-07-20 | 2023-09-12 | 浙江钦堂钙业有限公司 | Modified shell-core structure calcium carbonate with flame retardant function |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057367A (en) * | 1989-04-19 | 1991-10-15 | The Furukawa Electric Co., Ltd. | Flame retardant and a flame-retardant resin composition containing the same |
| JP2011137184A (en) * | 2011-04-15 | 2011-07-14 | Nippon Unicar Co Ltd | Blooming restraining method for flame-retardant resin composition |
| CN102746533A (en) * | 2012-07-11 | 2012-10-24 | 四川石棉巨丰粉体有限公司 | Heavy calcium carbonate composite packing as well as preparation method and application thereof |
-
2014
- 2014-02-17 CN CN201410052412.XA patent/CN103773082B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057367A (en) * | 1989-04-19 | 1991-10-15 | The Furukawa Electric Co., Ltd. | Flame retardant and a flame-retardant resin composition containing the same |
| JP2011137184A (en) * | 2011-04-15 | 2011-07-14 | Nippon Unicar Co Ltd | Blooming restraining method for flame-retardant resin composition |
| CN102746533A (en) * | 2012-07-11 | 2012-10-24 | 四川石棉巨丰粉体有限公司 | Heavy calcium carbonate composite packing as well as preparation method and application thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059392A (en) * | 2014-05-27 | 2014-09-24 | 池州凯尔特纳米科技有限公司 | Porous material modified calcium carbonate and preparation method thereof |
| CN104059392B (en) * | 2014-05-27 | 2015-07-01 | 池州凯尔特纳米科技有限公司 | Porous material modified calcium carbonate and preparation method thereof |
| CN104387615A (en) * | 2014-12-08 | 2015-03-04 | 太原理工大学 | Preparation method of magnesium hydroxide-coated talcum powder composite flame-retardant filler |
| CN104403372A (en) * | 2014-12-08 | 2015-03-11 | 广西利升石业有限公司 | Dry-process preparation method of superfine heavy calcium carbonate |
| CN104892980A (en) * | 2015-06-05 | 2015-09-09 | 葫芦岛首创科技有限公司 | Preparation method of nano-CaCO3-coated brucite composite material |
| CN104892980B (en) * | 2015-06-05 | 2017-08-11 | 葫芦岛首创科技有限公司 | In shepardite Surface coating Nano-meter CaCO33The preparation method of composite |
| CN106221291A (en) * | 2016-07-13 | 2016-12-14 | 凤台县泓瀚建筑防水材料厂 | The span of a kind of magnesium hydroxide cladding carrys out polyimide modified pearl filler |
| CN106395877A (en) * | 2016-08-30 | 2017-02-15 | 青岛食安生物工程有限公司 | Preparation process of pure natural nano-ultrafine calcium powders |
| CN109879302A (en) * | 2019-04-01 | 2019-06-14 | 东北大学 | Magnesium hydroxide/expansible graphite composite material method is prepared by raw material of magnesium carbonate mine |
| CN109879302B (en) * | 2019-04-01 | 2021-03-16 | 东北大学 | Method for preparing magnesium hydroxide/expandable graphite composite material by taking magnesium carbonate ore as raw material |
| CN110606500A (en) * | 2019-10-17 | 2019-12-24 | 四川新莱特新型建材有限公司 | Production process of calcium carbonate-magnesium oxide composite nano material |
| CN111048261A (en) * | 2019-10-21 | 2020-04-21 | 东莞福川精密工业股份有限公司 | Anti-aging flame-retardant cable and processing technology |
| CN113861664A (en) * | 2021-10-20 | 2021-12-31 | 荣威达光电(东莞)有限公司 | Wear-resistant flame-retardant TPU material and preparation method thereof |
| CN113845717A (en) * | 2021-11-16 | 2021-12-28 | 苏州亨利通信材料有限公司 | Low-cost waterproof low-smoke halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
| CN116514457A (en) * | 2023-05-23 | 2023-08-01 | 四川公路桥梁建设集团有限公司 | Flame-retardant asphalt mixture and preparation method thereof |
| CN116731397A (en) * | 2023-07-20 | 2023-09-12 | 浙江钦堂钙业有限公司 | Modified shell-core structure calcium carbonate with flame retardant function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103773082B (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103773082B (en) | Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler | |
| CN105860586B (en) | Precipitated magnesium carbonate | |
| CN102888020B (en) | Preparation method for brucite inorganic flame retardant | |
| RU2014151011A (en) | PRODUCTION AND APPLICATION OF A COMPOSITE STRUCTURE CONTAINING DEPOSITED CARBONATE | |
| CN102502749A (en) | Method for preparing rose calcium carbonate from low-grade limestone | |
| CN105314959B (en) | A kind of preparation method of Building Fire Protection ornament materials | |
| CN101177289A (en) | Method for preparing fibrous nano magnesium hydrate | |
| CN107445187A (en) | A kind of preparation method of oyster shell whiting modified calcium carbonate | |
| CN101747909B (en) | Method for preparing flame-retardant calcium carbonate | |
| CN106433222B (en) | A kind of preparation method and its product of composite flame-proof filler | |
| CN107446158A (en) | Enhanced complex phase crystal preparation method based on calcite and aragonite | |
| CN104628301B (en) | A kind of artificial stone utilizing lime-flue gas method brine sludge to manufacture | |
| CN103936013B (en) | A kind of method preparing white carbon black slurries | |
| CN111422894B (en) | Preparation method of calcium carbonate coated calcium carbonate powder | |
| CN101229925A (en) | Method for preparing magnesium hydroxide with coproduction of calcium chloride | |
| CN113636565A (en) | Method for preparing industrial vermiculite from phlogopite under normal pressure and industrial vermiculite | |
| CN110342552B (en) | Method for preparing active micro-nano magnesium hydroxide flame retardant by chemical method | |
| Tu et al. | Waste to resource: preparation of an efficient adsorbent and its sustainable utilization in flame retardant polyurethane composites | |
| WO2018178980A1 (en) | Compressed salt objects | |
| JP5107493B2 (en) | Method for producing calcium carbonate | |
| KR20130008286A (en) | A method for preparing caco3 using egg-shell | |
| CN109735018A (en) | A kind of antibacterial ceiling composite material and preparation method | |
| CN102115618B (en) | Extinction barium and preparation method thereof | |
| CN104961426A (en) | Fireproof door core | |
| CN109694208B (en) | Powder curing agent for expanded perlite insulation board and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140507 Assignee: Yunnan macro innovation Mstar Technology Ltd Assignor: China University of Mining & Technology, Beijing Contract record no.: 2016990000190 Denomination of invention: Preparation method of magnesium-hydroxide-coated calcium carbonate inorganic composite flame retardant filler Granted publication date: 20150401 License type: Exclusive License Record date: 20160509 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |