CN112795019B - Phenyl sulfonic acid silicone oil ester flame retardant and preparation method thereof - Google Patents
Phenyl sulfonic acid silicone oil ester flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phenyl sulfonic acid silicone oil ester flame retardant and a preparation method thereof, wherein the phenyl sulfonic acid silicone oil ester flame retardant has the following chemical structural formula:
in the formula: r1Is H or CH3，R2Is CH2CH2CH2Or CH2CH2CH2OCH2CH2. In order to improve the hydrolysis resistance of the flame-retardant material, the invention selects the benzenesulfonate group with better hydrophobicity, and the introduction of the benzenesulfonate group into polysiloxane can simultaneously improve the flame-retardant ability and the thermal stability; meanwhile, in order to improve the flame retardant capability of polysiloxane, a sulfur-containing group is introduced on the polysiloxane, and the sulfur-containing modified group is benzene sulfonyl chloride or p-methyl benzene sulfonyl chloride and has higher anti-reflection performanceThe long-chain silicone oil with hydroxyl-terminated groups is selected as the organopolysiloxane, the long-chain silicone oil has high thermal stability while reaction activity is maintained, and the hydroxyl groups are also easily modified, so that the flame retardant property, the thermal stability and the hydrolysis resistance of the material are improved in a synergistic manner.
Description
Technical Field
The invention relates to a high-molecular flame retardant and a preparation method thereof, in particular to a phenyl sulfonic acid silicone oil ester flame retardant and a preparation method thereof.
Background
In order to meet the requirements of fire protection of polymer materials, various flame retardant technologies have been proposed, wherein the addition of flame retardants is an effective method. The traditional sulfur-containing flame retardant mainly comprises potassium diphenylsulfone sulfonate (KSS), trichlorobenzene Sulfonate (STB), potassium perfluorobutane sulfonate (KPFBS) and the like, but the traditional sulfonate flame retardant has the problems of easy hydrolysis, poor weather resistance and the like and is expensive. In recent years, silicon-containing compounds are receiving more and more attention and are considered as "environment-friendly" flame retardants, but inorganic silicon materials are not well compatible with high polymer materials, and mechanical properties of the high polymer materials are often reduced. The organosilicon compound is relatively easy to disperse in the high polymer material, but the single use of the organosilicon compound can hardly make the high polymer material achieve the flame retardant effect. In order to solve the problems of the sulfur-containing flame retardant and the silicon-containing flame retardant, the synthesis of a novel sulfur-silicon flame retardant is particularly important.
In view of the defects of the existing silicon flame retardant, the inventor of the invention has abundant practical experience and professional knowledge based on years of the design and manufacture of the product, skillfully utilizes a chemical mechanism, continuously researches and innovates in practice, creates a phenyl sulfonic acid silicone oil ester flame retardant and a preparation method thereof, and improves the flame retardant effect and the stability on the basis of not changing the mechanical property of a high polymer material.
Disclosure of Invention
The first purpose of the invention is to provide a phenylsulfonic acid silicone oil ester flame retardant, which improves the flame retardant capability and the thermal stability.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a phenyl silicon sulfonate oil ester flame retardant, which has the following chemical structural formula:
in the formula: r1Is H or CH3，R2Is CH2CH2CH2Or CH2CH2CH2OCH2CH2。
The flame retardant capability and the thermal stability can be improved simultaneously by introducing the benzene sulfonate group into the polysiloxane, and meanwhile, in order to improve the flame retardant capability of the polysiloxane, the sulfur-containing group is introduced into the polysiloxane.
The second purpose of the invention is to provide a preparation method of the phenyl silicone sulfonate fire retardant, the operation is simpler and more convenient by improving the preparation process, and the prepared phenyl silicone sulfonate fire retardant has better fire retardant capability and thermal stability.
The technical purpose of the invention is realized by the following technical scheme:
the preparation method of the phenyl sulfonic acid silicone oil ester flame retardant comprises the following operation steps,
adding 1, 4-dioxane, hydroxyl-terminated silicone oil and an acid-binding agent into a three-neck flask provided with a heating and magnetic stirring device and a spherical condenser, slowly adding a 1, 4-dioxane mixed solution of phenylsulfonyl chloride into the three-neck flask through a constant-pressure dropping funnel under magnetic stirring, after dropwise adding, reacting at low temperature, heating and reacting, wherein the reaction is carried out in a nitrogen atmosphere; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and then washing with water for multiple times; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Further preferably, the molar ratio of the hydroxyl-terminated silicone oil to the phenylsulfonyl chloride is 1:2.0 to 2.4. In the reaction, the excess of the phenyl sulfonyl chloride is 0 to 0.2 times, which is beneficial to the complete reaction of the hydroxyl-terminated silicone oil as far as possible and improves the yield.
Further preferably, the phenylsulfonyl chloride is benzene sulfonyl chloride or p-methylbenzenesulfonyl chloride, and the sulfur-containing modifying group is benzene sulfonyl chloride or p-methylbenzenesulfonyl chloride. Benzene sulfonyl chloride and p-methyl benzene sulfonyl chloride can be dissolved in most organic solvents, and the range of selectable solvents is wide; the reaction activity of the benzene sulfonyl chloride and the p-methyl benzene sulfonyl chloride is high, and nucleophilic substitution reaction is easy to carry out.
More preferably, the terminal hydroxyalkyl silicone oil is terminal hydroxypropyl silicone oil or terminal hydroxyethyl ether group silicone oil. The terminal hydroxyl alkyl has higher activity and is easy to modify. The silicone oil with the end group of the carbon chain has good thermal stability, and the thermal stability can be further improved after the end capping. Different organic groups are adopted to carry out end capping modification on the silicone oil, so that the compatibility of the silicone oil with different high polymer materials can be improved.
As a further preference, the acid-binding agent is triethylamine, and the dosage of the acid-binding agent is 1.5 times of the molar dosage of the phenylsulfonyl chloride.
Further preferably, the dropping rate of the 1, 4-dioxane solution of phenylsulfonyl chloride is 12 to 60 drops/min. The reaction is exothermic, and the excessively high dripping speed in the early stage easily causes local overheating of the reaction liquid, increases side reactions and is not favorable for stable reaction; too slow a dropping rate may result in a prolonged reaction time.
As a further preference, this reaction is a nucleophilic substitution reaction of an acid chloride with a hydrocarbon hydroxyl group. The concentration of reactants is higher in the early stage of reaction, in order to control the reaction rate and reduce side reactions, the ice water bath is selected as the early stage reaction temperature, and the reaction time is 6-12 h.
More preferably, the reaction temperature is 60-90 ℃ and the reaction time is 12-18h for improving the reaction activity in the middle and later stages of the reaction.
As a further preference, to obtain a relatively pure product, the washing procedure is as follows: firstly, washing for three times by using 0.1mol/L sodium hydroxide solution to remove residual acyl chloride and benzenesulfonic acid by-products; secondly, washing for three times by using 0.1mol/L hydrochloric acid solution to remove residual triethylamine; and thirdly, washing for three times by using distilled water to remove residual triethylamine hydrochloride and a small amount of residual acid and alkali in the first step and the second step.
In conclusion, the phenyl sulfonic acid silicone oil ester flame retardant and the preparation method thereof provided by the invention have the following beneficial effects:
1) for sulfonate flame retardants, sulfonate groups in the sulfonate flame retardants are the key to enable high flame retardant capability of a high polymer material, but the sulfonate groups are hydrophilic and are easy to hydrolyze and migrate in a humid environment, so that the flame retardant capability of the material is reduced, and in order to improve the hydrolysis resistance of the flame retardant material, the invention selects benzenesulfonate groups with better hydrophobicity, and introduces the benzenesulfonate groups into polysiloxane to simultaneously improve the flame retardant capability and the thermal stability; meanwhile, in order to improve the flame retardant capability of polysiloxane, a sulfur-containing group is introduced into polysiloxane, a sulfur-containing modified group is benzene sulfonyl chloride or p-methyl benzene sulfonyl chloride and has high reaction activity, and organopolysiloxane is long-chain silicone oil with hydroxyl-terminated group, the long-chain silicone oil has high thermal stability while maintaining the reaction activity, and the hydroxyl-terminated group is also easily modified, so that the flame retardant property, the thermal stability and the hydrolysis resistance of the material are improved in a synergistic manner.
2) The benzenesulfonic acid silicone oil ester flame retardant synthesized by the method is a halogen-free flame retardant and is environment-friendly; meanwhile, the operation steps for synthesizing the benzenesulfonic acid silicone oil ester are simple, and the benzenesulfonic acid silicone oil ester can be synthesized by a one-pot method, so that the preparation cost is saved;
3) by adopting the preparation materials of the invention, the synergistic effect is realized, the synthesized silicon oil benzenesulfonate has better compatibility with the applied high molecular polymer, has less influence on the mechanical properties of the materials, and is suitable for popularization and application.
Drawings
FIG. 1 is a synthetic route of DBSSO of the invention;
FIG. 2 is an infrared spectrum (FTIR) of the silicone benzenesulfonate DBSSO of the present invention, wherein BSCl is benzenesulfonyl chloride, DHSO is hydroxy ethylen-propylene ether-terminated silicone oil, and DBSSO is silicone benzenesulfonate;
FIG. 3 shows the nuclear magnetic hydrogen of silicone oil benzenesulfonate DBSSO of the present invention1H NMR) spectrum;
FIG. 4 is a TGA of the DBSSO of the present invention.
Detailed Description
To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the phenyl silicone sulfonate fire retardant and the preparation method thereof according to the present invention are as follows.
In the present invention, the synthesis steps of DBSSO are shown in FIG. 1:
example 1
Adding 36g (0.020mol) of hydroxyl ethylene propylene ether-terminated silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 6.12ml (0.048mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant-pressure dropping funnel, wherein the dropping speed is 12 drops/minute, reacting for 12 hours in an ice bath after the dropping is finished, then heating to 90 ℃ and reacting for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, transferring the solvent into a vacuum oven to dry for 12 hours, and finally obtaining yellowish oily liquid which is named as DBSSO.
Example 2
Adding 36g (0.020mol) of terminal hydroxypropyl silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 6.12ml (0.048mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant pressure dropping funnel, wherein the dropping speed is 24 drops/minute, reacting for 12 hours in an ice bath after the dropping is finished, then heating to 90 ℃ and reacting for 12 hours, and the reaction is carried out under a nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 3
Adding 36g (0.020mol) of terminal hydroxypropyl silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 6.12ml (0.048mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant pressure dropping funnel, wherein the dropping speed is 12 drops/minute, reacting in an ice bath for 12 hours after the dropping is finished, then heating to 90 ℃ for reacting for 18 hours, and reacting under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 4
Adding 36g (0.020mol) of hydroxyl ethylene propylene ether terminated silicone oil, 8.30ml (0.060mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 7.63g (0.040mol) of p-methylbenzenesulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant pressure dropping funnel, wherein the dropping speed is 60 drops/minute, reacting for 6 hours in ice bath after the dropping is finished, then heating to 60 ℃ and reacting for 12 hours, and the reaction is carried out under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 5
Adding 36g (0.020mol) of hydroxyl ethylene propylene ether-terminated silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 9.15g (0.048mol) of p-methylbenzenesulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant-pressure dropping funnel, wherein the dropping speed is 30 drops/minute, reacting for 12 hours in ice bath after the dropping is finished, then heating to 90 ℃ and reacting for 12 hours, and the reaction is carried out under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 6
Adding 36g (0.020mol) of hydroxyl ethylene propylene ether-terminated silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 9.15g (0.048mol) of p-methylbenzenesulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant-pressure dropping funnel, wherein the dropping speed is 30 drops/minute, reacting for 12 hours in ice bath after the dropping is finished, then heating to 90 ℃ and reacting for 18 hours, and the reaction is carried out under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 7
Adding 36g (0.020mol) of ethylene propylene ether terminated silicone oil, 8.30ml (0.060mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 5.10ml (0.040mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant pressure dropping funnel at a dropping speed of 12 drops/minute, reacting for 6 hours in an ice bath after dropping is finished, and then heating to 60 ℃ for reacting for 12 hours, wherein the reaction is carried out in a nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
Example 8
Adding 36g (0.020mol) of end hydroxypropyl silicone oil, 8.30ml (0.060mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 5.10ml (0.040mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant pressure dropping funnel, wherein the dropping speed is 12 drops/minute, reacting for 6 hours in an ice bath after the dropping is finished, then heating to 60 ℃ for reacting for 12 hours, reacting all the time in a nitrogen atmosphere, performing suction filtration after the reaction is finished, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with diluted sodium hydroxide, diluted hydrochloric acid and distilled water for three times; and finally, distilling under reduced pressure to remove the solvent, and transferring into a vacuum oven to dry for 12 hours to obtain yellowish oily liquid.
Example 9
Adding 36g (0.020mol) of hydroxyl ethylene propylene ether-terminated silicone oil, 10.0ml (0.072mol) of triethylamine and 40ml of 1, 4-dioxane into a three-neck flask, adding a mixed solution of 6.12ml (0.048mol) of benzene sulfonyl chloride and 20ml of 1, 4-dioxane into the three-neck flask through a constant-pressure dropping funnel, wherein the dropping speed is 12 drops/minute, reacting for 12 hours in an ice bath after the dropping is finished, then heating to 90 ℃ and reacting for 18 hours, wherein the reaction is carried out under the nitrogen atmosphere all the time; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and washing with dilute sodium hydroxide, dilute hydrochloric acid and distilled water for three times respectively; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
The results of the performance tests on the flame retardant prepared in example 1 are as follows:
the results of the infrared test (fig. 2) analysis of the silicone oil benzenesulfonate (DBSSO) are as follows:
FTIR(KBr，cm-1)，2963，2906(-CH3，-CH2-)，1378，1187(-SO2-ph)，1261(Si-C)，1100-1000(Si-O-Si)。
nuclear magnetic hydrogen spectrum (figure 3) of silicon oil benzene sulfonate (DBSSO) test results are as follows:
H-NMR(400MHz,CDCl3)，δ(ppm)：7.5-8.0(-Ph)，7.3(CDCl3),3.70，3.64，3.43(-S-O-CH2-，C-CH2-O-，C-O-CH2-C)，1.6(C-CH2-C)，0.5-0.6(C-CH2-Si)，0(Si-CH3)。
the results of thermogravimetric analysis tests (fig. 4) under nitrogen atmosphere are as follows:
initial decomposition temperature (T)5％) 361 ℃, 434 ℃ for the maximum decomposition rate in the first stage and 567 ℃ for the maximum decomposition rate in the second stage.
Example 1 flame retardant performance test (table 1) the results are shown in table 1 below:
TABLE 1 PC, PC/1DBSSO and PC/2DBSSO vertical burn (UL-94) data and Limiting Oxygen Index (LOI) data
a, the reference standard of the vertical burning test is ASTM D3801, and the specification of the sample is 130X 13X 3.0 mm.
The limiting oxygen index is ASTM D2863, and the sample size is 130X 6.5X 3.0 mm.
The limit oxygen index of pure PC is 25.3%, the primary and secondary combustion time is 6s and 9s, which shows that PC has certain flame retardant capability, but PC also drops during combustion, and the flame retardant grade is V-2 grade. When 1 wt% DBSSO is added, the PC/1DBSSO composite sample does not drip when burning, the limiting oxygen index reaches 28.2%, and the flame retardant grade is V-1 grade. After 2 wt% of DBSSO is added, the PC/2DBSSO composite material shows the best flame retardant effect, the sum of the primary combustion time and the secondary combustion time is less than 10s, no dripping occurs during combustion, the flame retardant grade reaches V-0, and the limiting oxygen index is increased to 30.3% from 25.3% of pure PC.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a phenylsulfonic acid silicone oil ester flame retardant is characterized by comprising the following steps: comprises the following operation steps of the following steps of,
adding 1, 4-dioxane, hydroxyl-terminated silicone oil and an acid binding agent into a three-neck flask provided with a heating and magnetic stirring device and a spherical condenser, slowly adding a 1, 4-dioxane mixed solution of phenylsulfonyl chloride into the three-neck flask through a constant-pressure dropping funnel under magnetic stirring, after dropwise adding, reacting at low temperature, heating and reacting, wherein the reaction is carried out under the nitrogen atmosphere; after the reaction is finished, carrying out suction filtration, distilling the filtrate under reduced pressure to remove the solvent, diluting with dichloromethane, and then washing with water; and finally, distilling under reduced pressure to remove the solvent, and transferring to a vacuum oven for drying for 12 hours to obtain yellowish oily liquid.
2. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: the molar ratio of the phenyl sulfonyl chloride to the hydroxyl-terminated silicone oil is 2.0-2.4: 1.
3. the method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1 or 2, characterized in that: the phenylsulfonyl chloride is benzene sulfonyl chloride or p-methylbenzenesulfonyl chloride.
4. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1 or 2, characterized in that: the hydroxyl-terminated silicone oil is hydroxyl-terminated silicone oil or hydroxyl ethylene propylene ether-terminated silicone oil.
5. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: the acid-binding agent is triethylamine, and the dosage of the acid-binding agent is 1.5 times of the molar dosage of the phenylsulfonyl chloride.
6. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: the dropping speed of the 1, 4-dioxane solution of the phenylsulfonyl chloride is 12-60 drops/min.
7. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: the low-temperature reaction temperature is ice water bath, and the reaction time is 6-12 h.
8. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: the heating reaction temperature is 60-90 ℃, and the reaction time is 12-18 h.
9. The method for preparing the silicone oil phenylsulfonate flame retardant according to claim 1, characterized in that: and the washing operation is respectively carried out for three times by using dilute sodium hydroxide solution, dilute hydrochloric acid and distilled water.
10. A phenylsulfonic acid silicone oil ester flame retardant is characterized in that: the preparation method of any one of claims 1 to 9.
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