CN113174000B - Preparation method of poly (pentabromobenzyl acrylate) with controllable molecular weight - Google Patents
Preparation method of poly (pentabromobenzyl acrylate) with controllable molecular weight Download PDFInfo
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Abstract
The invention provides a preparation method of poly (pentabromobenzyl acrylate) with controllable molecular weight, which solves the technical problems of complicated reaction steps, difficult obtainment and high price of raw materials, low investment yield, uneven molecular weight distribution and unsuitability for industrial production of the existing preparation method of the poly (pentabromobenzyl acrylate). The invention can be widely applied to the technical field of flame retardant preparation.
Description
Technical Field
The application belongs to the technical field of fire retardant preparation, and particularly relates to a preparation method of pentabromobenzyl polyacrylate with controllable molecular weight.
Background
The pentabromobenzyl polyacrylate is a high-molecular bromine flame retardant, the flame retardant is provided with a pentabromobenzyl branched chain, the bromine content of the flame retardant is higher than 70%, and the acrylic acid part has a plurality of advantages: the flame retardant material has good compatibility and processability with a flame-retardant material, plays a role of a processing aid, enhances the weather resistance and the thermal stability of the flame retardant material, has the effects of fatigue resistance, flex resistance and whitening resistance and can improve the impact strength of the material; the material has excellent chemical resistance and electrical property, and is not easy to frost in use. The poly (pentabromobenzyl acrylate) is well compatible with high polymer and reinforcing material, does not migrate and frost in base material, is necessary for synthetic material in the fields of military industry, textile, electronics, electricity, construction and the like, and is particularly suitable for engineering plastics for manufacturing complex electronic equipment. Meanwhile, the pentabromobenzyl polyacrylate does not release carcinogens such as dioxin during combustion, and has stronger competitive advantage compared with other novel flame retardants.
At present, the synthesis of the polypentabromobenzyl acrylate mainly takes toluene, bromine (or bromine-containing compounds) and acrylic acid as raw materials, and the reaction is gradually carried out under certain conditions. Firstly, reacting toluene with bromine to prepare pentabromotoluene, reacting the pentabromotoluene with bromine (or bromine-containing compounds) to obtain pentabromobenzyl bromide, further reacting the pentabromobenzyl bromide with acrylic acid to prepare pentabromobenzyl acrylate monomer, and finally carrying out polymerization reaction on the pentabromobenzyl acrylate under the action of an initiator to generate the pentabromobenzyl polyacrylate. However, in the prior art, the synthesis process of the pentabromobenzyl polyacrylate has more intermediate reaction steps, and the purity and color of the product in each step are mainly affected, especially the pentabromotoluene is synthesized by adopting a high-temperature reaction, and in addition, the existing purification process is imperfect, so that the final product has low yield, uneven molecular weight distribution and low heat resistance.
Disclosure of Invention
The invention aims to solve the defects in the background technology, and provides a preparation method of the controlled molecular weight poly (pentabromobenzyl acrylate), which has the characteristics of controllable molecular weight, few reaction steps and high product yield, and the prepared poly (pentabromobenzyl acrylate) has excellent heat resistance.
Therefore, the invention provides a preparation method of the poly-controlled molecular weight pentabromobenzyl acrylate, which comprises the following steps:
(1) electrophilic substitution reaction: adding anhydrous bromine and aluminum trichloride into an organic solvent, then dripping benzyl chloride, controlling the reaction temperature and the reaction time, and carrying out substitution reaction to obtain pentabromobenzyl chloride, wherein the reaction equation is as follows:
(2) nucleophilic substitution reaction: directly adding a catalyst and a sodium acrylate solution into the pentabromobenzyl chloride prepared in the step (1) without separation, controlling the reaction temperature and the reaction time, and carrying out nucleophilic substitution reaction to prepare the pentabromobenzyl acrylate, wherein the reaction equation is as follows:
(3) polymerization reaction: adding a composite catalyst into the pentabromobenzyl acrylate prepared in the step (2), and controlling the reaction temperature, the reaction time and the dosage of the composite catalyst to perform polymerization reaction to prepare the molecular weight controllable poly (pentabromobenzyl acrylate) with the number average molecular weight (M) n ) Is 3000-20000, weight average molecular weight (M) W ) For 20000-50000, the reaction equation is as follows:
preferably, in the electrophilic substitution reaction in the step (1), the organic solvent is one or more of dichloroethane, tetrachloroethane, trichloromethane, carbon tetrachloride and dioxane.
Preferably, in the electrophilic substitution reaction in the step (1), the reaction temperature is 10-30 ℃, and the reaction time is 1-2 h.
Preferably, in the nucleophilic substitution reaction in the step (2), the catalyst is a quaternary ammonium salt, and the quaternary ammonium salt is one or more of tetrabutylammonium bromide and tetraethylammonium bromide.
Preferably, in the nucleophilic substitution reaction in step (2), the sodium acrylate solution is prepared by reacting acrylic acid and sodium carbonate, wherein the molar ratio of the acrylic acid to the sodium carbonate is 1: (1-1.05), and the pH value of the sodium acrylate solution is 7-9.
Preferably, in the nucleophilic substitution reaction in the step (2), the reaction temperature is 50-110 ℃, and the reaction time is 2-6 h.
Preferably, in the polymerization reaction in the step (3), the composite catalyst is a mixture of two or more of sodium persulfate, ammonium persulfate, potassium persulfate, Azobisisobutyronitrile (AIBN), and Benzoyl Peroxide (BPO).
Preferably, in the polymerization reaction in the step (3), the amount of the composite catalyst is 1 to 10 weight percent of the benzyl chloride.
Preferably, in the polymerization reaction in the step (3), the reaction temperature is 50-90 ℃ and the reaction time is 3-6 h.
The beneficial effects of the invention are as follows:
(1) the invention relates to a preparation method of poly (pentabromobenzyl acrylate) with controllable molecular weight, which takes benzyl chloride and anhydrous bromine as initial raw materials to carry out electrophilic substitution reaction, nucleophilic substitution reaction andthe polymerization reaction to obtain the pentabromobenzyl polyacrylate simplifies the operation steps of the traditional process, has the total yield of 93.37 percent, low cost, mild reaction conditions, easy control, stable product quality, controllable molecular weight and number average molecular weight (M) n ) 3000- W ) 20000-50000. In the preparation process of the product, a specific reaction control agent and reaction conditions are adopted in each step, so that the yield of the product in each step is improved, and the conversion rate and the heat resistance of the final product are greatly improved.
(2) The preparation method of the poly (pentabromobenzyl acrylate) with controllable molecular weight has the advantages of cheap and easily obtained raw materials, mild reaction conditions, simple and convenient operation, obviously shortened integral reaction steps, low cost, suitability for industrial production, accordance with the environment-friendly and energy-saving idea pursued at present, obviously improved total yield and obvious progress compared with the prior art.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a gel liquid chromatogram of a polypentabromobenzyl polyacrylate obtained in example 1;
FIG. 2 is a gel liquid chromatogram of a pentabromobenzyl polyacrylate obtained in example 2;
FIG. 3 is a gel liquid chromatogram of a polypentabromobenzyl polyacrylate obtained in example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
Example 1
(1) Electrophilic substitution reaction: adding 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane into a reaction kettle, cooling to 10 ℃, slowly dripping 100g of benzyl chloride into the reaction kettle, controlling the temperature in the reaction kettle to be 10 ℃ in the dripping process, absorbing tail gas by using water, preserving the temperature for 1h after finishing dripping, and carrying out electrophilic substitution reaction to obtain the pentabromobenzyl chloride, wherein the yield is 98.2%, and the purity is more than 99%.
(2) Nucleophilic substitution reaction: reacting 75g of acrylic acid with 550g of 20% sodium carbonate solution at room temperature to prepare a sodium acrylate solution, and adjusting the pH value to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, then cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 50 ℃, preserving heat for 6 hours to perform nucleophilic substitution reaction, after finishing the heat preservation, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining pentabromobenzyl acrylate with the yield of 95.56% and the purity of more than 99%.
(3) Polymerization reaction: and (3) adding 0.5g of Azobisisobutyronitrile (AIBN) and 0.5g of Benzoyl Peroxide (BPO) serving as composite catalysts into the organic layer obtained in the step (2), heating to 50 ℃, preserving heat for 6 hours to perform polymerization reaction, cooling to normal temperature after heat preservation is finished, performing suction filtration, and drying wet materials to obtain the pentabromobenzyl polyacrylate with the yield of 97.30%.
In summary, the overall yield of the reaction was 91.31%.
Example 2
(1) Electrophilic substitution reaction: adding 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane into a reaction kettle, cooling to 10 ℃, slowly dripping 100g of benzyl chloride into the reaction kettle, controlling the temperature in the reaction kettle to be 20 ℃ in the dripping process, absorbing tail gas by using water, preserving the temperature for 1.5 hours after finishing dripping, and carrying out electrophilic substitution reaction to obtain the pentabromobenzyl chloride, wherein the yield is 98.79%.
(2) Nucleophilic substitution reaction: reacting 75g of acrylic acid with 565g of 20% sodium carbonate solution at room temperature to prepare sodium acrylate solution, and adjusting the pH value to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, then cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 80 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after finishing the heat preservation, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining pentabromobenzyl acrylate with the yield of 96.78%.
(3) Polymerization reaction: and (3) adding 0.5g of Azodiisobutyronitrile (AIBN) and 0.5g of Benzoyl Peroxide (BPO) into the organic layer obtained in the step (2) to serve as a composite catalyst, heating to 70 ℃, preserving heat for 4.5 hours to perform polymerization reaction, cooling to normal temperature after heat preservation is finished, performing suction filtration, and drying wet materials to obtain the pentabromobenzyl polyacrylate with the yield of 97.66%.
In summary, the overall reaction yield was 93.37%.
Example 3
(1) Electrophilic substitution reaction: adding 700g of anhydrous bromine, 5g of catalyst aluminum trichloride and 550g of dichloroethane into a reaction kettle, cooling to 10 ℃, slowly dripping 100g of benzyl chloride into the reaction kettle, controlling the temperature in the reaction kettle to be 30 ℃ in the dripping process, absorbing tail gas by using water, preserving the temperature for 2 hours after the dripping is finished, and carrying out electrophilic substitution reaction to obtain the pentabromobenzyl chloride, wherein the yield is 98.12%.
(2) Nucleophilic substitution reaction: reacting 75g of acrylic acid with 580g of 20% sodium carbonate solution at room temperature to prepare sodium acrylate solution, and adjusting the pH value to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, then cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 110 ℃, preserving heat for 2 hours to perform nucleophilic substitution reaction, after finishing the heat preservation, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining pentabromobenzyl acrylate with the yield of 95.77%.
(3) Polymerization reaction: and (3) adding 0.5g of Azobisisobutyronitrile (AIBN) and 0.5g of sodium persulfate serving as composite catalysts into the organic layer obtained in the step (2), heating to 90 ℃, keeping the temperature for 3 hours to perform polymerization reaction, cooling to normal temperature after the heat preservation is finished, performing suction filtration, and drying wet materials to obtain the polypentabromobenzyl polyacrylate with the yield of 97.25%.
In summary, the overall reaction yield was 91.39%.
The control group 1 is a preparation method of the poly (pentabromobenzyl acrylate) with controllable molecular weight, which comprises the following steps:
(1) electrophilic substitution reaction: adding 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane into a reaction kettle, cooling to 10 ℃, slowly dripping 100g of benzyl chloride into the reaction kettle, controlling the temperature in the reaction kettle to be 60 ℃ in the dripping process, absorbing tail gas by using water, preserving the temperature for 1.5 hours after finishing dripping, and carrying out electrophilic substitution reaction to obtain the pentabromobenzyl chloride, wherein the yield is 82.11%.
(2) Nucleophilic substitution reaction: 75g of acrylic acid and 565g of 20 percent sodium carbonate solution react at room temperature to prepare sodium acrylate solution, and the pH value is adjusted to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 80 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after the heat preservation is finished, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining the pentabromobenzyl acrylate with the yield of 86.54%.
(3) Polymerization reaction: and (3) adding 2.5g of Azodiisobutyronitrile (AIBN) and 2.5g of Benzoyl Peroxide (BPO) into the organic layer obtained in the step (2) as a composite catalyst, heating to 70 ℃, preserving heat for 4.5 hours to perform polymerization reaction, cooling to normal temperature after heat preservation is finished, performing suction filtration, and drying wet materials to obtain the pentabromobenzyl polyacrylate with the yield of 83.11%.
In summary, the overall yield of the reaction was 59.06%.
Control group 2
(1) Electrophilic substitution reaction: 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane are added into a reaction kettle, the temperature is reduced to 10 ℃, 100g of benzyl chloride is slowly dripped into the reaction kettle, the temperature in the reaction kettle is controlled to be 20 ℃ in the dripping process, tail gas is absorbed by water, the temperature is kept for 1.5h after the dripping is finished, electrophilic substitution reaction is carried out, and the yield is 98.56%.
(2) Nucleophilic substitution reaction: 75g of acrylic acid and 565g of 20 percent sodium carbonate solution react at room temperature to prepare sodium acrylate solution, and the pH value is adjusted to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 150 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after the heat preservation is finished, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining pentabromobenzyl acrylate with the yield of 82.89%.
(3) Polymerization reaction: and (3) adding 0.5g of Azodiisobutyronitrile (AIBN) and 0.5g of Benzoyl Peroxide (BPO) into the organic layer obtained in the step (2) to serve as a composite catalyst, controlling the temperature to be 70 ℃, preserving the heat for 4.5 hours to perform a polymerization reaction, cooling to normal temperature after the heat preservation is finished, performing suction filtration, and drying wet materials to obtain the pentabromobenzyl polyacrylate with the yield of 80.54%.
In summary, the overall yield of the reaction was 65.80%.
Control group 3
(1) Electrophilic substitution reaction: 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane are added into a reaction kettle, the temperature is reduced to 10 ℃, 100g of benzyl chloride is slowly dripped into the reaction kettle, the temperature in the reaction kettle is controlled to be 20 ℃ in the dripping process, tail gas is absorbed by water, the temperature is kept for 1.5h after the dripping is finished, electrophilic substitution reaction is carried out, and the yield is 98.34%.
(2) Nucleophilic substitution reaction: reacting 75g of acrylic acid with 565g of 20% sodium carbonate solution at room temperature to prepare sodium acrylate solution, and adjusting the pH value to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 80 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after the heat preservation is finished, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, layering and taking an organic layer for later use to obtain pentabromobenzyl acrylate, wherein the yield is 96.05%.
(3) Polymerization reaction: and (3) adding 5g of AIBN and 5g of Benzoyl Peroxide (BPO) serving as composite catalysts into the organic layer obtained in the step (2), heating to 120 ℃, preserving heat for 4.5 hours to perform polymerization reaction, cooling to normal temperature after heat preservation is finished, performing suction filtration, and drying wet materials to obtain the polypentabromobenzyl acrylate, wherein the yield is 83.72%.
In summary, the overall reaction yield was 79.08%.
Control 4(1) electrophilic substitution reaction: 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane are added into a reaction kettle, the temperature is reduced to 10 ℃, 100g of benzyl chloride is slowly dripped into the reaction kettle, the temperature in the reaction kettle is controlled to be 20 ℃ in the dripping process, tail gas is absorbed by water, the temperature is kept for 1.5h after the dripping is finished, electrophilic substitution reaction is carried out, and the yield is 98.66%.
(2) Nucleophilic substitution reaction: 75g of acrylic acid and 565g of 20 percent sodium carbonate solution react at room temperature to prepare sodium acrylate solution, and the pH value is adjusted to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 80 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after the heat preservation is finished, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, layering and taking an organic layer for later use to obtain pentabromobenzyl acrylate, wherein the yield is 96.72%.
(3) Polymerization reaction: and (3) adding 1g of Azobisisobutyronitrile (AIBN) serving as a catalyst into the organic layer obtained in the step (2), heating to 70 ℃, preserving heat for 4.5 hours to perform polymerization reaction, cooling to normal temperature after heat preservation is finished, performing suction filtration, and drying wet materials to obtain the polypentabromobenzyl acrylate, wherein the yield is 86.54%.
In summary, the overall reaction yield was 82.58%.
Control group 5
(1) Electrophilic substitution reaction: 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane are added into a reaction kettle, the temperature is reduced to 10 ℃, 100g of benzyl chloride is slowly dripped into the reaction kettle, the temperature in the reaction kettle is controlled to be 20 ℃ in the dripping process, tail gas is absorbed by water, the temperature is kept for 1.5h after the dripping is finished, electrophilic substitution reaction is carried out, and the yield is 98.60%.
(2) Nucleophilic substitution reaction: 75g of acrylic acid and 565g of 20 percent sodium carbonate solution react at room temperature to prepare sodium acrylate solution, and the pH value is adjusted to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, then cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 80 ℃, preserving heat for 4 hours to perform nucleophilic substitution reaction, after finishing the heat preservation, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, and layering to obtain an organic layer for later use, thereby obtaining pentabromobenzyl acrylate with the yield of 96.54%.
(3) Polymerization reaction: and (3) adding 1g of Benzoyl Peroxide (BPO) serving as a composite catalyst into the organic layer obtained in the step (2), heating to 70 ℃, preserving the temperature for 4.5 hours to perform polymerization reaction, cooling to normal temperature after the heat preservation is finished, performing suction filtration, and drying wet materials to obtain the polypentabromobenzyl acrylate, wherein the yield is 88.14%.
In summary, the overall reaction yield was 83.90%.
Control group 6
(1) Electrophilic substitution reaction: adding 640g of anhydrous bromine, 0.5g of catalyst aluminum trichloride and 250g of dichloroethane into a reaction kettle, cooling to 10 ℃, slowly dripping 100g of benzyl chloride into the reaction kettle, controlling the temperature in the reaction kettle to be 10 ℃ in the dripping process, absorbing tail gas by using water, preserving the temperature for 1h after finishing dripping, and carrying out electrophilic substitution reaction to obtain the pentabromobenzyl chloride, wherein the yield is 98.15%.
(2) Nucleophilic substitution reaction: reacting 75g of acrylic acid with 580g of 20% sodium carbonate solution at room temperature to prepare sodium acrylate solution, and adjusting the pH value to 7-9; heating the pentabromobenzyl chloride solution prepared in the step (1), evaporating excessive bromine and residual hydrobromic acid, cooling to below 50 ℃, adding 1g of tetrabutylammonium bromide into a reaction kettle, heating to 50 ℃, preserving heat for 2 hours to perform nucleophilic substitution reaction, after finishing preserving heat, adding 150g of water, stirring and washing at 30 ℃ for 0.5 hour, layering and taking an organic layer for later use to obtain pentabromobenzyl acrylate, wherein the yield is 95.89%.
(3) Polymerization reaction: and (3) adding 10g of sodium persulfate serving as a catalyst into the organic layer obtained in the step (2), heating to 90 ℃, preserving the temperature for 3 hours to perform polymerization reaction, cooling to normal temperature after the heat preservation is finished, performing suction filtration, and drying wet materials to obtain the pentabromobenzyl polyacrylate with the yield of 88.05%.
In summary, the overall yield of the reaction was 82.87%.
The above are only examples of the present invention, for example, in the electrophilic substitution reaction in step (1), the organic solvent is any one of tetrachloroethane, trichloromethane, carbon tetrachloride and dioxane; in the polymerization reaction in the step 3, the composite catalyst is a mixture of two or more of sodium persulfate, ammonium persulfate, potassium persulfate, AIBN and BPO, and the preparation method of the pentabromobenzyl polyacrylate can be realized.
Table 1 is a summary of the data for examples 1-3 and controls 1-6
| Temperature of nucleophilic substitution reaction | Temperature of nucleophilic substitution reaction | Temperature of polymerization | Polymerization catalyst | Yield of electrophilic substitution | Nucleophilic substitution reaction yield | Yield of polymerization | Final yield | |
| Example 1 | 10℃ | 50℃ | 50℃ | AIBN+BPO | 98.20％ | 95.56％ | 97.30％ | 91.31％ |
| Example 2 | 20 |
80 |
70℃ | AIBN+BPO | 98.79％ | 96.78％ | 97.66％ | 93.37％ |
| Example 3 | 30℃ | 110 |
90℃ | AIBN + sodium persulfate | 98.12％ | 95.77％ | 97.25％ | 91.39％ |
| Control group 1 | 60 |
80 |
70℃ | AIBN+BPO | 82.11％ | 86.54％ | 83.11％ | 59.06％ |
| Control group 2 | 20℃ | 150 |
70℃ | AIBN+BPO | 98.56％ | 82.89％ | 80.54％ | 65.80％ |
| Control group 3 | 20 |
80℃ | 120℃ | AIBN+BPO | 98.34％ | 96.05％ | 83.72％ | 79.08％ |
| Control group 4 | 20 |
80 |
70℃ | AIBN | 98.66％ | 96.72％ | 86.54％ | 82.58％ |
| Control group 5 | 20 |
80 |
70℃ | BPO | 98.60％ | 96.54％ | 88.14％ | 83.90％ |
| Control group 6 | 30℃ | 110 |
90℃ | Sodium persulfate | 98.15％ | 95.89％ | 88.05％ | 82.87％ |
As can be seen from the data in table 1, it is understood from example 2 and control 1 that the electrophilic substitution reaction temperature is 10 to 30 ℃, the yield of pentabromobenzyl ester is the highest, and when the yield of pentabromobenzyl ester is higher than 30 ℃, the conversion rate of pentabromobenzyl ester is low, and the yield of nucleophilic substitution reaction and polymerization reaction are reduced after the yield of pentabromobenzyl ester is reduced, which fully proves that the conversion rate of pentabromobenzyl ester influences the conversion rate of pentabromobenzyl acrylate and pentabromobenzyl polyacrylate, resulting in the reduction of the final yield.
It is understood from example 2 and control 2 that the reaction yield of the pentabromobenzyl acrylate is highest at the nucleophilic substitution reaction temperature of 50-110 ℃, and that the conversion of pentabromobenzyl acrylate is decreased at a temperature higher than 110 ℃, and the polymerization yield is also decreased when the conversion of pentabromobenzyl acrylate is decreased, resulting in a decrease in the final yield.
It is understood from example 2 and control 3 that the reaction yield of the polypentabromobenzyl acrylate is highest at a polymerization temperature of 70-90 deg.C, and that the conversion of the polypentabromobenzyl acrylate is lowered at a temperature higher than 90 deg.C, resulting in a lowered final yield in the polymerization reaction of step 3.
As is clear from examples 2 and comparative examples 4 to 5 and examples 3 and comparative example 6, the yield of the composite catalyst used in the polymerization reaction of the present invention is higher than that of the single catalyst.
Heat resistance test
(1) The polypentabromobenzyl polyacrylates prepared in examples 1 to 3 were subjected to gel liquid chromatography analysis, respectively, as shown in FIGS. 1 to 3,
in FIG. 1, the final polymer has a narrow molecular weight distribution and a number average molecular weight (hereinafter referred to as M) n ) 9140 weight average molecular weight (hereinafter referred to as M) W ) 30100.
In FIG. 2, the final polymer has a narrow molecular weight distribution, M n Is 1.10X 10 4 ，M w Is 3.72X 10 4 。
In FIG. 3, the final polymer has a narrow molecular weight distribution, M n Is 1.79X 10 4 ，M w Is 4.45X 10 4 。
As can be seen from FIGS. 1 to 3, the molecular weight distribution of the polypentabromobenzyl polyacrylate obtained by the present invention is narrow, and the number average molecular weight (M) thereof is n ) 3000- W ) 20000-50000, low thermal weight loss and good heat resistance.
(2) The polypentabromobenzyl polyacrylates prepared in examples 1-3 were subjected to free bromine detection, TAG detection and the detection data are shown in Table 2
Table 2 shows the data of the heat resistance tests of examples 1 to 3
| Free bromine | 0.1% thermal weight loss temperature | 0.5% thermal weight loss temperature | 1% thermal weight loss temperature | |
| Example 1 | ≤5ppm | 303℃ | 314℃ | 320℃ |
| Example 2 | ≤5ppm | 309℃ | 319℃ | 342℃ |
| Example 3 | ≤5ppm | 305℃ | 316℃ | 326℃ |
| Control group 4 | ≤5ppm | 280.3℃ | 305.2℃ | 315.5℃ |
As can be seen from the data in Table 2, the maximum temperature of 0.1% thermal weight loss of the polypentabromobenzyl acrylate prepared by the method is 309 ℃, 319 ℃ of 0.5% thermal weight loss, 342 ℃ of 0.5% thermal weight loss, which is obviously higher than that of the control group 4, and the result fully proves that the polypentabromobenzyl acrylate prepared by the method has excellent heat resistance.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. A preparation method of a controlled molecular weight poly (pentabromobenzyl acrylate) is characterized by comprising the following steps:
(1) electrophilic substitution reaction: adding anhydrous bromine and aluminum trichloride into an organic solvent, then dripping benzyl chloride, controlling the reaction temperature to be 10-30 ℃ and the reaction time to be 1-2h, and carrying out substitution reaction to obtain pentabromobenzyl chloride, wherein the reaction equation is as follows:
(2) nucleophilic substitution reaction: directly adding a catalyst and a sodium acrylate solution into the pentabromobenzyl chloride prepared in the step (1) without separation, controlling the reaction temperature to be 50-110 ℃ and the reaction time to be 2-6h, and carrying out nucleophilic substitution reaction to prepare the pentabromobenzyl acrylate, wherein the reaction equation is as follows:
(3) polymerization reaction: adding a composite catalyst into the pentabromobenzyl acrylate prepared in the step (2), and controlling the reaction temperature and the reaction time to perform polymerization reaction to prepare the molecular weight controllable poly (pentabromobenzyl acrylate) with the number average molecular weight (M) n ) 3000- W ) 20000-50000, the composite catalyst is a mixture of two or more of sodium persulfate, ammonium persulfate, potassium persulfate, Azobisisobutyronitrile (AIBN) and Benzoyl Peroxide (BPO), and the reaction equation is as follows:
2. the method for preparing poly (pentabromobenzyl acrylate) according to claim 1, wherein in the electrophilic substitution of step (1), the organic solvent is one or more of dichloroethane, tetrachloroethane, trichloromethane, carbon tetrachloride and dioxane.
3. The method for preparing poly (pentabromobenzyl acrylate) of claim 1, wherein in the nucleophilic substitution reaction in step (2), the catalyst is quaternary ammonium salt, and the quaternary ammonium salt is one or more of tetrabutylammonium bromide and tetraethylammonium bromide.
4. The method for preparing poly (pentabromobenzyl acrylate) of claim 1, wherein in the nucleophilic substitution reaction in step (2), the sodium acrylate solution is prepared by reacting acrylic acid with sodium carbonate at a molar ratio of 1: (1-1.05), and the pH value of the sodium acrylate solution is 7-9.
5. The method for preparing pentabromobenzyl polyacrylates according to claim 1 wherein in the polymerization reaction of step (3), the amount of said composite catalyst is 1 to 10% by weight of benzyl chloride.
6. The process for preparing pentabromobenzyl polyacrylate of controlled molecular weight according to claim 1, wherein in the polymerization reaction of step (3), the reaction temperature is 50-90 ℃ and the reaction time is 3-6 h.
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| US4211730A (en) * | 1975-06-21 | 1980-07-08 | Dynamit Nobel Aktiengesellschaft | Acrylate-based polymers and copolymers and their use as flameproofing agents |
| SE421072B (en) * | 1975-06-21 | 1981-11-23 | Dynamit Nobel Ag | POLYMERS ON THE BASIS OF PENTABROMBENZYL ESTERS AND TETRABROMXYLYLENE ESTERS AND USE THEREOF AS A FLAMMABLE PROTECTION AGENT |
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