CN104262679A - Sulfonate fire retardant and preparation method thereof - Google Patents
Sulfonate fire retardant and preparation method thereof Download PDFInfo
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- CN104262679A CN104262679A CN201410525053.5A CN201410525053A CN104262679A CN 104262679 A CN104262679 A CN 104262679A CN 201410525053 A CN201410525053 A CN 201410525053A CN 104262679 A CN104262679 A CN 104262679A
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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 materials, particularly relate to a kind of Sulfonates fire retardant and preparation method thereof.
Background technology
Flame retardant is as one of the crucial additive of transparent PC engineering plastics, and play dual function that is fire-retardant and that strengthen, the quality of its performance directly affects the performance and used life of transparent PC engineering plastics.
At present, the flame retardant that PC engineering plastics are conventional mainly contains halogen system, silicon system, nitrogen-phosphorus system, boron system and sulfonate system.Halogenated flame retardant can produce a large amount of cigarettes and corrosive gases when burning, can to environment.Silicon-series five-retardant is the environmentally friendly fire retardant of a class, and it has the advantages such as efficient LSZH, but it is expensive, and the stability of product needs to improve further, usual and other fire retardant compound uses.Nitrogen-phosphorus type flame retardant addition is large, perishable mould.Boron flame retardant flame retardant effect is not good.Sulfonates fire retardant has efficiently because of it, clean environment firendly, adds the feature such as use properties, color and luster not affecting goods in material to and be widely used in various material.But current industrial common several Sulfonates fire retardants are (as perfluorobutyl potassium, 2; 4; 5 trichlorobenzene sodium sulfonates, potassium phenylsulphonyl benzene sulfonate) ubiquity the problem such as synthesis route and aftertreatment complexity, and also there is certain room for promotion in flame retardant properties.
Chinese patent CN102977575A discloses a kind of Sulfonates fire retardant containing triazine ring structure, this based flame retardant not only has the general advantage of the Sulfonates flame retardant of Current commercial, and its Heat stability is good and with low cost, operational path is simple, the effect of cooperative flame retardant can also be formed with nitrogen simultaneously.But its aftertreatment is still more complicated, flame retardant properties needs to be improved further, to expand the scope of application of modified PC.
Therefore, need to seek more effective, simple and direct method, preparation has the clean and environment-friendly transparent PC Sulfonates fire retardant of excellent fire-retardancy.
Summary of the invention
The invention provides a kind of Sulfonates fire retardant and preparation method thereof, a difficult problem for Sulfonates fire retardant operational path and aftertreatment complexity in prior art can be overcome, and improve flame retardant properties further.
The invention provides a kind of Sulfonates fire retardant, its structural formula is as follows:
Wherein, R
ffor 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 is dissolved in solvent DMF and is made into the solution that concentration is 4wt% ~ 6wt%, above-mentioned solution is placed in the container of-20 ~-45 DEG C, adds the phenyl aldehyde of same alkali equimolar amount under nitrogen protection, stir 40-60 minute;
(2) raw material A adding same alkali equimolar amount is reacted, and be stirred to and terminate reaction, described raw material A structural formula is
wherein R
ffor fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl (be the Chinese patent of CN101193856A see publication number);
(3) temperature of reaction is down to room temperature, suction filtration, filter cake freeze-day with constant temperature is obtained Sulfonates fire retardant.
Described alkali is one or more in tertiary butyl potassium alcoholate, sodium hydride, boryl lithium or boronation trisodium.
After adding raw material A, the stirring reaction time is 2 ~ 3 hours.
Described suction filtration adopts acetoneand ethyl acetate repetitive scrubbing suction filtration.
The inventive method reaction process and aftertreatment simple and direct, due to the special construction of obtained fire retardant, the synergy of fluorochemicals and aromatic sulphonate, makes its flame retardant properties excellent performance, has good thermally-stabilised and chemical stability.Add in transparent PC and can not change its transparency and gloss.
Halogen Sulfonates fire retardant provided by the invention compared with prior art has the following advantages:
(1) Sulfonates fire retardant provided by the invention contains fluorine element, can also form the effect of cooperative flame retardant, have good flame retardant properties with fluorine;
(2) reaction process of Sulfonates fire retardant provided by the invention and aftertreatment simple and direct;
(3) Sulfonates fire retardant provided by the invention combines the advantage of fluorochemicals and aromatics, has good thermodynamic stability;
(4) add a small amount of Sulfonates fire retardant provided by the invention and can reach good flame retardant effect, therefore, add the use properties, color and luster etc. that do not affect goods in Sulfonates fire retardant to material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 4wt% in dinethylformamide, place it in the round-bottomed flask of-20 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 40 minutes, then add 19.64g structural formula and be
raw material A, stir after 2 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 2
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 4wt% in dinethylformamide, place it in the round-bottomed flask of-30 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 50 minutes, then add 19.64g structural formula and be
raw material A, stir after 3 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 3
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 4wt% in dinethylformamide, place it in the round-bottomed flask of-45 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 40 minutes, then add 19.64g structural formula and be
raw material A, stir after 2 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 4
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 5wt% in dinethylformamide, place it in the round-bottomed flask of-20 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 50 minutes, then add 36.34 grams of structural formulas and be
raw material A, stir after 3 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 5
The sodium hydride of 10 grams is dissolved in solvent N; be made into the solution that concentration is 5wt% in dinethylformamide, place it in the round-bottomed flask of-20 DEG C, add the phenyl aldehyde of same sodium hydride equimolar amount under nitrogen protection; stir 40 minutes, then add 91.83 grams of structural formulas and be
raw material A, stir after 2.5 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 6
10 grams of sodium hydrides are dissolved in solvent DMF and are made into the solution that concentration is 6wt%, place it in the round-bottomed flask of-30 DEG C, add the phenyl aldehyde of same sodium hydride equimolar amount under nitrogen protection, stir 60 minutes, then add 91.83 grams of structural formulas and be
raw material A, stir after 2.5 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 7
10 grams of sodium hydrides are dissolved in solvent DMF and are made into the solution that concentration is 6wt%, place it in the round-bottomed flask of-45 DEG C, add the phenyl aldehyde of same sodium hydride equimolar amount under nitrogen protection, stir 40 minutes, then add 91.83 grams of structural formulas and be
raw material A, stir after 3 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 8
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 6wt% in dinethylformamide, place it in the round-bottomed flask of-20 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 50 minutes, then add 26.47 grams of structural formulas and be
raw material A, stir after 3 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 9
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 6wt% in dinethylformamide, place it in the round-bottomed flask of-30 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 40 minutes, then add 26.47 grams of structural formulas and be
raw material A, stir after 2 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Embodiment 10
10 grams of tertiary butyl potassium alcoholates are dissolved in solvent N; be made into the solution that concentration is 6wt% in dinethylformamide, place it in the round-bottomed flask of-40 DEG C, add the phenyl aldehyde of same tertiary butyl potassium alcoholate equimolar amount under nitrogen protection; stir 60 minutes, then add 26.47 grams of structural formulas and be
raw material A, stir after 2 hours terminate reaction.Be down to room temperature, suction filtration, with acetoneand ethyl acetate repetitive scrubbing suction filtration, filter cake be drying to obtain at a constant temperature described Sulfonates fire retardant.
Show after tested, the Sulfonates fire retardant that the present embodiment obtains can make PC Flame Retardancy can reach UL-94V-0 level (3.2mm is thick) when addition is 0.07%--0.3wt% in transparent PC.
Above-described embodiment does not limit the present invention in any way, and the technical scheme that the mode that every employing is equal to replacement or equivalent transformation obtains all drops in protection scope of the present invention.
Claims (5)
1. a Sulfonates fire retardant, is characterized in that structural formula is as follows:
Wherein, R
ffor fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl.
2. a preparation method for Sulfonates fire retardant, is characterized in that comprising the following steps:
(1) alkali is dissolved in solvent DMF and is made into the solution that concentration is 4wt% ~ 6wt%, above-mentioned solution is placed in the container of-20 ~-45 DEG C, adds the phenyl aldehyde of same alkali equimolar amount under nitrogen protection, stir 40-60 minute;
(2) raw material A adding same alkali equimolar amount is reacted, and be stirred to and terminate reaction, described raw material A structural formula is
wherein R
ffor fluoro-alkyl, perfluoroalkyl, ring fluoroalkyl or ring perfluoroalkyl;
(3) temperature of reaction is down to room temperature, suction filtration, filter cake freeze-day with constant temperature is obtained Sulfonates fire retardant.
3. the preparation method of Sulfonates fire retardant according to claim 2, is characterized in that: described alkali is one or more in tertiary butyl potassium alcoholate, sodium hydride, boryl lithium or boronation trisodium.
4. the preparation method of Sulfonates fire retardant according to claim 2, is characterized in that: after adding raw material A, and the stirring reaction time is 2 ~ 3 hours.
5. the preparation method of Sulfonates fire retardant according to claim 2, is characterized in that: described suction filtration adopts acetoneand ethyl acetate repetitive scrubbing suction filtration.
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| Application Number | Priority Date | Filing Date | Title |
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| 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 true CN104262679A (en) | 2015-01-07 |
| CN104262679B 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 |
|---|
| 欧育湘，等: "含硫化合物阻燃聚碳酸酯及其阻燃机理", 《塑料科技》 * |
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