CN104262679B - Sulfonate fire retardant and preparation method thereof - Google Patents
Sulfonate fire retardant and preparation method thereof Download PDFInfo
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- CN104262679B CN104262679B CN201410525053.5A CN201410525053A CN104262679B CN 104262679 B CN104262679 B CN 104262679B CN 201410525053 A CN201410525053 A CN 201410525053A CN 104262679 B CN104262679 B CN 104262679B
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Abstract
The invention discloses a sulfonate fire retardant and a preparation method thereof. The structural formula of the fire retardant is shown as a formula (in the Specification). The preparation method of the sulfonate fire retardant comprises the following steps: dissolving alkali into a solvent N,N-dimethylformamide to prepare a solution of which the concentration is 4-6 weight percent; putting the solution into a container of which the temperature is minus 20-minus 45 DEG C, adding benzaldehyde of which the molar weight is equal to that of the alkali under the protection of nitrogen, and stirring for 40-60 minutes; adding a raw material A of which the molar weight is equal to that of the alkali for reaction, and stirring until the reaction is finished, wherein in the structural formula of the raw material A, Rf is a fluoroalkyl group, a perfluoroalkyl group, a cyclofluoroalkyl group or a cycloperfluoroalkyl group; reducing the reaction temperature to the room temperature, performing suction filtration, and drying a filter cake at the constant temperature to obtain the sulfonate fire retardant. According to the method, the reaction process and the after-treatment process are simple. Due to the special structure of the obtained fire retardant, the sulfonate fire retardant is excellent in fire retardant property, high in thermal stability and high in chemical stability under the synergistic action of fluorinated compounds and aromatic sulfonates. After the sulfonate fire retardant is added into transparent PC (Polycarbonate), the transparency and the gloss of transparent PC cannot be changed.
Description
Technical field
The present invention relates to organic synthesis material and refractory material, more particularly to a kind of Sulfonates fire retardant and its preparation
Method.
Background technology
Flame retardant plays fire-retardant and enhanced double action as one of the crucial additive of transparent PC engineering plastics,
The quality of its performance directly affects the performance and used life of transparent PC engineering plastics.
At present, the conventional flame retardant of PC engineering plastics mainly has halogen system, silicon systems, nitrogen-phosphorus system, boron system and sulfonate system.
Halogenated flame retardant can produce substantial amounts of cigarette and corrosive gas in burning, and environment can be polluted.Silicon-series five-retardant is one
The environmentally friendly fire retardant of class, it has the advantages that efficient LSZH, but its is expensive, and the stability of product also has
Treat in further raising, generally with other fire retardant compound uses.Nitrogen-phosphorus type flame retardant addition is big, perishable mould.Boron system
Fire retardant effect on driving birds is not good.Sulfonates fire retardant because its have efficiently, clean environment firendly, be added in material and do not influence product
Performance, color and luster the features such as be widely used in various materials.But common several Sulfonateses resistance industrial at present
Combustion agent (such as perfluorobutyl potassium sulfonate, 2,4,5 trichlorine benzene sulfonic acid sodium salts, potassium phenylsulphonyl benzene sulfonate) generally existing synthesis technique road
The problems such as line and complicated post processing, and also there is certain room for promotion in fire resistance.
Chinese patent CN102977575A discloses a kind of Sulfonates fire retardant containing triazine ring structure, and such is fire-retardant
Agent not only with Current commercial Sulfonates flame retardant general advantage, and its heat endurance it is good and with low cost,
Process route is simple, while the effect of cooperative flame retardant can also be formed with nitrogen.But, its still more complicated, anti-flammability of post processing
Further raising can be needed, to expand the scope of application of modified PC.
Accordingly, it would be desirable to seek method more effectively, simple and direct, the clean and environment-friendly with excellent fire-retardancy is prepared transparent
PC Sulfonates fire retardants.
The content of the invention
The present invention provides a kind of Sulfonates fire retardant and preparation method thereof, and Sulfonates in the prior art can be overcome to hinder
Combustion agent process route and the complicated problem of post processing, and further improve fire resistance.
The present invention provides a kind of Sulfonates fire retardant, and its structural formula is as follows：
Wherein, RfIt is fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl.
The preparation method of Sulfonates fire retardant of the present invention, comprises the following steps：
(1) alkali soluble is made into the solution that concentration is 4wt%~6wt% in solvent DMF, will be above-mentioned
Solution is placed in -20~-45 DEG C of container, and the benzaldehyde of same alkali equimolar amounts, 40-60 points of stirring are added under nitrogen protection
Clock；
(2) add and reacted with the raw material A of alkali equimolar amounts, stirring is to reaction, the raw material A structural formula is terminatedWherein RfIt is fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl (referring to publication number
It is the Chinese patent of CN101193856A)；
(3) reaction temperature is down to room temperature, filter cake freeze-day with constant temperature is obtained Sulfonates fire retardant by suction filtration.
The alkali is one or more in tert-butyl group potassium alcoholate, sodium hydride, boryl lithium or boronation trisodium.
After adding raw material A, the stirring reaction time is 2~3 hours.
The suction filtration uses acetoneand ethyl acetate cyclic washing suction filtration.
The inventive method reaction process and post processing are simple and direct, due to the special construction of resulting fire retardant, fluorochemical
With the synergy of aromatic sulphonate so that its fire resistance excellent performance, with good thermally-stabilised and chemical stability.
Being added in transparent PC will not change its transparency and gloss.
The Halogen Sulfonates fire retardant that the present invention is provided has advantages below compared with prior art：
(1) the Sulfonates fire retardant that the present invention is provided contains fluorine element, and the effect of cooperative flame retardant can also be formed with fluorine,
With preferable fire resistance；
(2) reaction process of the Sulfonates fire retardant that the present invention is provided and post processing are simple and direct；
(3) the Sulfonates fire retardant that the present invention is provided combines the advantage of fluorochemical and aromatic compound, tool
There is good thermodynamic stability；
(4) the Sulfonates fire retardant for adding a small amount of present invention offer can reach good flame retardant effect, therefore, addition
Sulfonates fire retardant is not to influenceing performance, color and luster of product etc. in material.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 4wt%, by it
It is placed in -20 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 40 points
Clock, adding 19.64g structural formulas isRaw material A, stirring 2 hours after terminate reaction.It is down to room
Temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates resistance described in filter cake at a constant temperature drying to obtain
Combustion agent.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 2
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 4wt%, by it
It is placed in -30 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 50 points
Clock, adding 19.64g structural formulas isRaw material A, stirring 3 hours after terminate reaction.It is down to room
Temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates resistance described in filter cake at a constant temperature drying to obtain
Combustion agent.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 3
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 4wt%, by it
It is placed in -45 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 40 points
Clock, adding 19.64g structural formulas isRaw material A, stirring 2 hours after terminate reaction.It is down to room
Temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates resistance described in filter cake at a constant temperature drying to obtain
Combustion agent.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 4
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 5wt%, by it
It is placed in -20 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 50 points
Clock, adding 36.34 grams of structural formulas isRaw material A, stirring 3 hours after terminate reaction.
It is down to room temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the sulfonic acid described in filter cake at a constant temperature drying to obtain
Salt based flame retardant.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 5
10 grams of sodium hydride is dissolved in solvent DMF the solution for being made into that concentration is 5wt%, is put
In -20 DEG C of round-bottomed flask, the benzaldehyde of same sodium hydride equimolar amounts is added under nitrogen protection, stirred 40 minutes, then add
Entering 91.83 grams of structural formulas isRaw material A, stirring 2.5 hours after terminate reaction.Room temperature is down to, is taken out
Filter, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates fire retardant described in filter cake at a constant temperature drying to obtain.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 6
10 grams of sodium hydrides are dissolved in solvent DMF the solution for being made into that concentration is 6wt%, place it in-
In 30 DEG C of round-bottomed flask, the benzaldehyde of same sodium hydride equimolar amounts is added under nitrogen protection, stirred 60 minutes, add
91.83 grams of structural formulas areRaw material A, stirring 2.5 hours after terminate reaction.Room temperature is down to, is taken out
Filter, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates fire retardant described in filter cake at a constant temperature drying to obtain.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 7
10 grams of sodium hydrides are dissolved in solvent DMF the solution for being made into that concentration is 6wt%, place it in-
In 45 DEG C of round-bottomed flask, the benzaldehyde of same sodium hydride equimolar amounts is added under nitrogen protection, stirred 40 minutes, add
91.83 grams of structural formulas areRaw material A, stirring 3 hours after terminate reaction.It is down to room temperature, suction filtration,
With acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates fire retardant described in filter cake at a constant temperature drying to obtain.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 8
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 6wt%, by it
It is placed in -20 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 50 points
Clock, adding 26.47 grams of structural formulas isRaw material A, stirring 3 hours after terminate reaction.It is down to
Room temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates described in filter cake at a constant temperature drying to obtain
Fire retardant.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 9
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 6wt%, by it
It is placed in -30 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 40 points
Clock, adding 26.47 grams of structural formulas isRaw material A, stirring 2 hours after terminate reaction.It is down to
Room temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates described in filter cake at a constant temperature drying to obtain
Fire retardant.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Embodiment 10
10 grams of tert-butyl group potassium alcoholates are dissolved in solvent DMF the solution for being made into that concentration is 6wt%, by it
It is placed in -40 DEG C of round-bottomed flask, the benzaldehyde of same tert-butyl group potassium alcoholate equimolar amounts is added under nitrogen protection, stirs 60 points
Clock, adding 26.47 grams of structural formulas isRaw material A, stirring 2 hours after terminate reaction.It is down to
Room temperature, suction filtration, with acetoneand ethyl acetate cyclic washing suction filtration, by the Sulfonates described in filter cake at a constant temperature drying to obtain
Fire retardant.
Test indicate that, the Sulfonates fire retardant that the present embodiment is obtained addition in transparent PC is 0.07%--
PC Flame Retardancies can be enable to reach UL-94V-0 grades (3.2mm is thick) during 0.3wt%.
Above-described embodiment limits the present invention never in any form, every to be obtained by the way of equivalent or equivalent transformation
Technical scheme all fall within protection scope of the present invention.
Claims (4)
1. a kind of Sulfonates fire retardant, it is characterised in that structural formula is as follows：
Wherein, RfIt is fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl.
2. a kind of preparation method of Sulfonates fire retardant, it is characterised in that comprise the following steps：
(1) alkali soluble is made into the solution that concentration is 4wt%~6wt% in solvent DMF, by above-mentioned solution
It is placed in -20~-45 DEG C of container, the benzaldehyde of same alkali equimolar amounts is added under nitrogen protection, stirs 40-60 minutes；
The alkali is one or more in tert-butyl group potassium alcoholate, sodium hydride, boryl lithium or boronation trisodium；
(2) add and reacted with the raw material A of alkali equimolar amounts, stirring is to reaction, the raw material A structural formula is terminatedWherein RfIt is fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl；
(3) reaction temperature is down to room temperature, filter cake freeze-day with constant temperature is obtained Sulfonates fire retardant by suction filtration.
3. the preparation method of Sulfonates fire retardant according to claim 2, it is characterised in that：After adding raw material A, stirring
Reaction time is 2~3 hours.
4. the preparation method of Sulfonates fire retardant according to claim 2, it is characterised in that：The suction filtration uses acetone
With ethyl acetate cyclic washing suction filtration.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410525053.5A CN104262679B (en) | 2014-10-08 | 2014-10-08 | Sulfonate fire retardant and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410525053.5A CN104262679B (en) | 2014-10-08 | 2014-10-08 | Sulfonate fire retardant and preparation method thereof |
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| CN104262679A CN104262679A (en) | 2015-01-07 |
| CN104262679B true CN104262679B (en) | 2017-05-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644612A (en) * | 2003-09-25 | 2005-07-27 | 大科能树脂有限公司 | Anti-static thermoplastic resin composition and shaped products therefrom |
| WO2007093513A1 (en) * | 2006-02-14 | 2007-08-23 | Ciba Holding Inc. | Aromatic sulphonate flame retardant compositions |
| CN101193856A (en) * | 2005-06-07 | 2008-06-04 | 纳幕尔杜邦公司 | Manufacture of hydrofluoroalkanesulfonic acids |
| CN102977575A (en) * | 2012-10-09 | 2013-03-20 | 中北大学 | Sulfonate fire retardation agents and preparation methods thereof |
-
2014
- 2014-10-08 CN CN201410525053.5A patent/CN104262679B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644612A (en) * | 2003-09-25 | 2005-07-27 | 大科能树脂有限公司 | Anti-static thermoplastic resin composition and shaped products therefrom |
| CN101193856A (en) * | 2005-06-07 | 2008-06-04 | 纳幕尔杜邦公司 | Manufacture of hydrofluoroalkanesulfonic acids |
| WO2007093513A1 (en) * | 2006-02-14 | 2007-08-23 | Ciba Holding Inc. | Aromatic sulphonate flame retardant compositions |
| CN102977575A (en) * | 2012-10-09 | 2013-03-20 | 中北大学 | Sulfonate fire retardation agents and preparation methods thereof |
Non-Patent Citations (1)
| Title |
|---|
| 含硫化合物阻燃聚碳酸酯及其阻燃机理;欧育湘，等;《塑料科技》;20071031;第35卷(第10期);42-45 * |
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