CN102977575A - Sulfonate fire retardation agents and preparation methods thereof - Google Patents

Abstract

The invention discloses a class of sulfonate flame retardants and a preparation method thereof, and relates to the technical field of synthesis of a class of sulfonate-containing flame retardants. The object of the present invention is to provide a class of sulfonate-containing flame retardants and a preparation method thereof in order to solve the deficiencies in the above-mentioned prior art. This type of flame retardant is non-toxic, anti-melt drop, smoke suppression, high flame retardant efficiency, good thermal stability, low cost, simple process route, adding to the material does not affect the performance, color, etc. of the product, and can also be used with Nitrogen forms a synergistic flame retardant effect. The structural formula of described a class of sulfonate-containing flame retardants is as follows: Among them, R can be aliphatic amines containing sulfonic acid groups, alcohols, aromatic amines or phenols containing sulfonic acid groups, and the like. The sulfonate-containing flame retardant described in the present invention can be completed through one-step nucleophilic substitution reaction, which not only simplifies the process, but also avoids the occurrence of multi-step post-treatment.

Description

A class of sulfonate flame retardant and preparation method thereof

technical field

The invention relates to the technical field of synthesis of a class of sulfonate-containing flame retardants. The sulfonate-containing flame retardant of the present invention contains a triazine ring structure. The invention also relates to a preparation method of the sulfonate-containing flame retardant.

Background technique

Flame retardants are a class of chemical synthetic substances added to various materials for the purpose of improving the fire and flame retardancy of materials. Currently reported and commercialized flame retardants are used in various materials. Although they have achieved different degrees of flame retardant performance, there are many defects in the process of use. It will produce a lot of smoke and corrosive gas, and some even produce carcinogenic dioxin; the addition of phosphorus-nitrogen flame retardants is large, which leads to the decline of the mechanical properties and mechanical properties of the material and is easy to corrode the mold; organosilicon flame retardants Although it has the advantages of non-toxic, smoke suppression, environmental protection and high efficiency, the common problems of this kind of flame retardants are that they are expensive, the technology is not mature enough, and the performance stability of the products needs to be further improved.

Sulfonate-containing flame retardants have the characteristics of high efficiency, non-toxicity, anti-melt droplets, and smoke suppression, and are used in various materials. It can not only effectively improve material processing, heat resistance, and improve mechanical properties of materials. High fuel efficiency, very little addition, anti-droplet dripping. Several commercial sulfonate flame retardants (such as sodium 2,4,5 trichlorobenzene sulfonate, potassium perfluorobutyl sulfonate, potassium benzenesulfonyl benzene sulfonate) that have been commercialized in the newspapers, their flame retardant The effect is very good. For example, adding 0.1% potassium perfluorobutane sulfonate to polycarbonate (PC) can increase the LOI value of the material from 24% to 37%, and the flame retardancy can reach V of UL-94. -0 grade (3.2mm) and does not change the transparency and mechanical properties of PC. However, the above-mentioned sulfonate flame retardants generally have problems such as high price, complex synthesis process route and post-treatment.

Contents of the invention

The object of the present invention is to provide a class of sulfonate-containing flame retardants and a preparation method thereof in order to solve the deficiencies in the above-mentioned prior art. This type of flame retardant is non-toxic, anti-melt drop, smoke suppression, high flame retardant efficiency, good thermal stability, low cost, simple process route, adding to the material does not affect the performance, color, etc. of the product, and can also be used with Nitrogen forms a synergistic flame retardant effect.

The purpose of the present invention is achieved through subordinate technical solutions:

The structural formula of described a class of sulfonate-containing flame retardants is as follows:

Among them, R can be aliphatic amines containing sulfonic acid groups, alcohols, aromatic amines or phenols containing sulfonic acid groups, and the like.

Preferred R is potassium taurine;

Preferred R is potassium p-aminobenzenesulfonate;

Preferred R is potassium 2,5-disulfonic acid benzenesulfonate;

A kind of preparation method containing sulfonate flame retardant of the present invention comprises the steps:

Dissolve cyanuric chloride in a solvent, then add organic amines, alcohols or phenols containing sulfonic acid groups, and gradually raise the temperature to 80-100°C. During the reaction, use KOH aqueous solution to adjust the pH value of the reaction system to maintain it at 7- 14. After the reaction is finished, cool down to room temperature, add a reverse-phase precipitant to the system to produce a large amount of white precipitate, filter with suction, and dry the filter cake at a constant temperature to obtain the sulfonate-containing flame retardant;

The molar ratio of the described cyanuric chloride to organic amines, alcohols, phenols and the like is 1: 3.0 to 3.6;

The amount of solvent per mole of cyanuric chloride is 500-2000ml;

The amount of the reverse phase precipitant is 5-10 times of the final volume of the reaction.

During the reaction process, the reaction progress is monitored by monitoring the pH value of the system.

In order to better realize the present invention, the solvent includes any one of water, acetone, dimethylformamide, and dimethyl sulfoxide;

The reverse phase precipitation reagent includes any one of ethanol, acetonitrile, ethyl acetate and tetrahydrofuran.

The reaction process of the present invention is:

Compared with the prior art, the present invention has the following advantages and beneficial effects:

A class of sulfonate-containing flame retardants described in the present invention can be completed through one-step nucleophilic substitution reaction, which saves unnecessary intermediate processes, simplifies the process, and avoids the occurrence of multi-step post-treatment; at the same time, the The raw materials of sulfonate flame retardants are abundant and cheap.

In terms of structure, the sulfonate-containing flame retardant of the present invention contains sulfonic acid groups and nitrogen in the molecule at the same time, and the two can play a synergistic flame retardant effect;

Description of drawings:

Figure 1 ESI (negative)-MS spectrum of flame retardant (I)

The infrared spectrogram of Fig. 2 flame retardant (I)

The proton nuclear magnetic resonance spectrum figure of Fig. 3 flame retardant (I)

The thermal weight loss diagram of Fig. 4 flame retardant (I)

Figure 5 ESI (negative)-MS of flame retardant (II)

The infrared spectrum of Fig. 6 flame retardant (II)

The H NMR spectrum of Fig. 7 flame retardant (II)

The thermogravimetric diagram of Fig. 8 flame retardant (II)

ESI (negative)-MS spectrum of Fig. 9 flame retardant (III)

The infrared spectrum of Fig. 10 flame retardant (III)

The proton nuclear magnetic resonance spectrum figure of Fig. 11 flame retardant (III)

The thermogravimetric diagram of Fig. 12 flame retardant (III)

Detailed ways

The present invention will be described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

A sulfonate-containing flame retardant having the following structure was prepared.

First, stir and dissolve 9.225g (0.05mol) of cyanuric chloride in 50ml of acetone in a four-neck flask, then add an aqueous solution containing 18.75g of taurine, and slowly raise the temperature of the system as the reaction progresses to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, add 6 times the volume of absolute ethanol, a large amount of white solids are precipitated during the process, filter with suction, wash the filter cake with a mixed solution of methanol: chloroform = 3: 2 (v/v), and wash the filter cake with ninhydrin The filtrate was tested until the taurine was completely removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield was 90.2%. The structural characterization data are as follows, and the specific spectra are shown in the accompanying drawings (Figures 1-4):

FT-IR data (KBr, cm ^-1 ): 3400 (vs NH), 2856 (-CH ₂ -), 1576 (-C=N-), 1184 and 1050 (-SO ₂ -).

ESI-MS (negative) (m/z) spectral data: 524.93443 (MK ⁺ ), 486.97991 (M-2K ⁺ +H), 449.02273 (M-3K ⁺ +2H).

¹ H-NMR (500M, d ₆ -DMSO): 2.61 ppm (singlet), 3.447 ppm (singlet), 6.296-6.529 ppm (triplet).

Flame retardant performance application: Add 0.3g of sulfonate-containing flame retardant to 500g of polycarbonate (bayer2805) to make flame-retardant polycarbonate, extrude through twin-screw extruder, granulate, and inject into standard Spline (standard is GB/T17037.1-1997). The combustion test shows that: at 750°C, the char formation rate of pure PC is 30.4%, while the char formation rate of modified PC is 19.96%; the limiting oxygen index (LOI%) of pure PC is 24, and UL-94 reaches V -Class 2, the LOI of the modified PC is 33.6, and the UL-94 reaches V-0.

Example 2

First, 9.225g (0.05mol) of cyanuric chloride is placed in a four-necked flask and stirred and dissolved in 50ml of water, then an aqueous solution containing 18.75g of aminoethanesulfonic acid is added, and the temperature of the system is slowly raised as the reaction progresses. up to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, add 6 times the volume of absolute ethanol, a large amount of white solids are precipitated during the process, filter with suction, wash the filter cake with a mixed solution of methanol: chloroform = 3: 2 (v/v), and wash the filter cake with ninhydrin The filtrate was tested until the taurine was completely removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield was 93.8%.

Example 3

First, stir and dissolve 9.225g (0.05mol) of cyanuric chloride in 50ml of water in a four-neck flask, then add an aqueous solution containing 18.75g of taurine, and slowly raise the temperature of the system as the reaction progresses to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, and adjust the pH of the final reaction solution to 2 with concentrated hydrochloric acid. During the process, a large amount of white solids precipitated, filtered with suction, washed with water and a mixed solution of methanol: chloroform = 3: 2 (v/v) and filtered cake, and the filtrate was tested with ninhydrin until taurine was removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield is 95%.

Example 4

Others are the same as in Example 1, and concentrated hydrochloric acid is used as the precipitating agent instead, and the productive rate is 93.1%.

Example 5

A sulfonate-containing flame retardant having the following structure was prepared.

First, stir and dissolve 9.225g (0.05mol) of cyanuric chloride in 50ml of water in a four-necked flask, then add an aqueous solution containing 25.95g of p-aminobenzenesulfonic acid, and slowly raise the temperature of the system as the reaction progresses. up to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, and adjust the pH of the final reaction solution to 2 with concentrated hydrochloric acid. During the process, a large amount of white solids precipitated, filtered with suction, washed with water and a mixed solution of methanol: chloroform = 3: 2 (v/v) and filtered cake, and the filtrate was tested with ninhydrin until the p-aminobenzenesulfonic acid was removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield is 95%. The structural characterization data are as follows, and the specific spectra are shown in the accompanying drawings (Figures 5-8):

FT-IR data (KBr, cm ^-1 ): 3400 (vs N-H), 1576 (-C=N-), 1184 and 1050 (-SO ₂ -).

ESI-MS (negative) (m/z) spectral data: 668.932 (MK ⁺ ), 630.978 (M-2K ⁺ +H).

¹ H-NMR (500M, d ₆ -DMSO): 7.536ppm (single peak, 6H), 7.759ppm (single peak, 6H), 9.37-11.25ppm (group peak, 3H).

Flame retardant performance application: Add 0.3g of sulfonate-containing flame retardant to 500g of polycarbonate (bayer2805) to make flame-retardant polycarbonate, extrude through twin-screw extruder, granulate, and inject into standard Spline (standard is GB/T17037.1-1997). The combustion test shows that: at 750°C, the char formation rate of pure PC is 30.4%, while the char formation rate of modified PC is 38.96%; the limiting oxygen index (LOI%) of pure PC is 24, and UL-94 reaches V -Class 2, the LOI of the modified PC is 34.3, and the UL-94 reaches V-0.

Example 6

First, stir and dissolve 9.225g (0.05mol) of cyanuric chloride into 50ml of acetone in a four-necked flask, then add an aqueous solution containing 25.95g of p-aminobenzenesulfonic acid, and slowly raise the temperature of the system as the reaction progresses. up to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, use acetonitrile as a reverse-phase precipitant, a large amount of white solids are precipitated during the process, filter with suction, wash the filter cake with water, methanol: chloroform = 3: 2 (v/v) mixed solution, and wash with nindan Test the filtrate for ketones until the sulfanilic acid is completely removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield was 95.3%.

Example 7

Others are the same as in Example 5, except that ethanol is used as the reverse phase precipitant, and the yield is 94.8%.

Example 8

A sulfonate-containing flame retardant having the following structure was prepared.

At first the cyanuric chloride of 9.225g (0.05mol) is stirred and dissolved in the acetone of 50ml in the four-necked flask, then adds the aqueous solution containing the 2 of 41.25g, the potassium of 5-disulfonic acid group benzene sulfonate, along with the progress of reaction Slowly raise the temperature of the system to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, use acetonitrile as a reverse-phase precipitant, a large amount of white solids are precipitated during the process, filter with suction, wash the filter cake with water, methanol: chloroform = 3: 2 (v/v) mixed solution, and wash the filter cake with ninhydrin The filtrate was tested for ketones until 2,5-disulfobenzenesulfonic acid was removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield is 95%. The structural characterization data are as follows, and the specific spectra are shown in the accompanying drawings (Figures 5-8):

FT-IR data (KBr, cm ^-1 ): 3400 (vs NH), 1576 (-C=N-), 1184 and 1050 (-SO ₂ -).

ESI-MS (negative) (m/z) spectrum data: 990.88777 (M-Na ⁺ ), 952.92939 (M-Na ⁺ -K ⁺ +H), 914.979961 (M-Na ⁺ -2K ⁺ +2H).

¹ H-NMR (500M, d ₆ -DMSO): 7.531-7.769 ppm (group peak, 9H), 9.375-9.538 ppm (group peak, 3H).

Flame retardant performance application: Add 0.3g of sulfonate-containing flame retardant to 500g of polycarbonate (bayer2805) to make flame-retardant polycarbonate, extrude through twin-screw extruder, granulate, and inject into standard Spline (standard is GB/T17037.1-1997). The combustion test shows that: at 750°C, the char formation rate of pure PC is 30.4%, while the char formation rate of modified PC is 29.5%; the limiting oxygen index (LOI%) of pure PC is 24, and UL-94 reaches V -Class 2, the LOI of the modified PC is 36.8, and the UL-94 reaches V-0.

Example 9

First the cyanuric chloride of 9.225g (0.05mol) is stirred and dissolved in the water of 50ml in the four-necked flask, then adds the aqueous solution containing 2,5-disulfonic acid group benzene sulfonate potassium, along with the progress of reaction Slowly raise the temperature of the system to 90°C. During the reaction process, the pH value of the system was monitored with a pH meter, and the pH value of the system was adjusted with KOH aqueous solution to keep it at about 9.

When the pH value of the system no longer changes, it marks the end of the reaction. Cool, concentrate under reduced pressure, use ethanol as a reverse-phase precipitant, a large amount of white solids are precipitated during the process, filter with suction, wash the filter cake with water, methanol: chloroform = 3: 2 (v/v) mixed solution, and use nindan The filtrate was tested for ketones until 2,5-disulfobenzenesulfonic acid was removed. Putting the white substance in a vacuum drying oven to dry at a constant temperature of 70°C is a sulfonate-containing flame retardant described in the present invention. The yield was 93.9%.

Example 10

Others are the same as in Example 8, but acetone is used as the solvent instead, and the yield is 95.8%.

Example 11

Others are the same as in Example 8, except that concentrated hydrochloric acid is used as the reverse phase precipitation agent, and the yield is 93.4%.

As described above, the present invention can be preferably carried out.

Claims (10)

1. a class sulfonate fire retardant, structural formula is as follows:

In, R can be for containing sulfonic aliphatic amide, alcohol and containing sulfonic aromatic amine or phenol.

2. a class hydrochlorate fire retardant according to claim 1 is characterized in that R is taurine potassium; R is Sulphanilic Acid potassium; R is 2,5-disulfonic acid base Phenylsulfonic acid potassium.

3. a class sulfonate fire retardant according to claim 1 is characterized in that sulfonate fire retardant structural formula is as follows:

。

4. a class sulfonate fire retardant according to claim 1 is characterized in that sulfonate fire retardant structural formula is as follows:

。

5. a class sulfonate fire retardant according to claim 1 is characterized in that sulfonate fire retardant structural formula is as follows:

。

6. a class contains the preparation method of sulfonate fire retardant, comprises the steps:

The cyanuric chloride solubilizing agent is dissolved, add again and contain sulfonic organic amine, alcohol or phenol, be warming up to gradually 80-100 ℃, use the pH value of KOH aqueous solution conditioned reaction system in the reaction process, make it maintain 7-14, reaction is down to room temperature after finishing, and adds anti-phase precipitation agent in system, produce a large amount of white precipitate materials, suction filtration with the filter cake freeze-day with constant temperature, namely obtains to contain the sulfonate fire retardant.

7. a described class contains the preparation method of sulfonate fire retardant according to claim 6, and the mol ratio that it is characterized in that described cyanuric chloride and organic amine, alcohol or phenol is 1: 3.0～3.6.

8. a described class contains the preparation method of sulfonate fire retardant according to claim 6, the solvent load that it is characterized in that described every mole of cyanuric chloride is 500～2000ml, and described solvent comprises any one in water, acetone, dimethyl formamide, the dimethyl sulfoxide (DMSO).

9. a described class contains the preparation method of sulfonate fire retardant according to claim 6, and the consumption that it is characterized in that described anti-phase precipitation agent is 5～10 times of the reaction final volume; Described anti-phase precipitation agent comprises any one in ethanol, acetonitrile, ethyl acetate, the tetrahydrofuran (THF).

10. a class contains the application of sulfonate fire retardant aspect fire-retardant.

Images