CN112831055A - Degradable flame-retardant polystyrene block copolymer and preparation method thereof - Google Patents
Degradable flame-retardant polystyrene block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a degradable flame-retardant polystyrene block copolymer material and a preparation method thereof; the polystyrene material with lasting flame retardant performance is obtained by blocking macromolecular flame retardant into a polystyrene molecular chain, in addition, a photosensitizer, a sun-screening agent and a degradation control agent are added into a block polymethacrylic acid and a polystyrene block copolymer on the polystyrene molecular chain, and the polymethacrylic acid and the degradation control agent interact to realize the rapid degradation of the polystyrene block copolymer.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a degradable flame-retardant polystyrene block copolymer and a preparation method thereof.
Background
Polystyrene is an organic hydrocarbon, has a limiting oxygen index of only 18.0 percent, and belongs to the field of combustible materials. Once ignited, at a temperature of 1.3-6.4 cm.min-1The combustion of the PS product generates a large amount of smoke, toxic gases and molten droplets, which is determined by the molecular structure of PS itself: the larger benzene ring on the side chain is easy to be burnt incompletely and removed when being heated, so that dense smoke and molten drops are formed; phase (C)Dense smoke and toxic gas are easy to suffocate and die for open fire, the foaming type styrene material is more serious when being subjected to fire, and the regular honeycomb-shaped and closed cell structure increases the air circulation and enables the combustion of the material to be easier.
The disposable polystyrene tableware and the expandable polystyrene packaging material are usually discarded within a short time after being used, and polystyrene products are difficult to degrade in natural environment, so that the problem of environmental pollution is easily caused; based on the above, the invention provides a degradable flame-retardant polystyrene block copolymer and a preparation method thereof.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a degradable flame-retardant polystyrene block copolymer and a preparation method thereof.
The invention aims to provide a degradable flame-retardant polystyrene block copolymer.
The invention also aims to provide a preparation method of the degradable flame-retardant polystyrene block copolymer.
The above purpose of the invention is realized by the following technical scheme:
vacuum drying the degradable flame-retardant polystyrene block copolymer at 80 ℃, adding 60-100 parts by mass of the degradable flame-retardant polystyrene block copolymer, 5 parts by mass of a photosensitizer, 5 parts by mass of a sun-screening agent and 5 parts by mass of a degradation control agent into an open type heat mill with a double-roller temperature of 235 ℃, uniformly mixing and discharging the materials after the materials are melted and coated on rollers, and carrying out hot pressing, cold pressing at room temperature and discharging on a flat vulcanizing machine at 240 ℃ to obtain the degradable flame-retardant polystyrene block copolymer material.
A degradable flame-retardant polystyrene block copolymer has a structural formula shown as the following formula (I):
in the formula, n is 15-30, m is 7-15, and P is 10-20.
The preparation method of the degradable flame-retardant polystyrene block copolymer comprises the following steps:
1. and (2) taking triethylamine as a catalyst and an acid-binding agent, chloroform as a reaction solvent, reacting diethyl dichlorophosphamide with ethylene glycol at the temperature of 60-70 ℃ for 4-6 h, continuously adding p-hydroxybenzoic acid for end capping, carrying out heat preservation and reflux for 2-3 h to finish the reaction, and carrying out reduced pressure distillation, suction filtration and extraction on the crude product to obtain the reaction type flame retardant terminal benzoic acid poly (diethylamino) ethylene phosphate.
Wherein the feeding molar ratio of the diethyl dichlorophosphamide to the glycol to the p-hydroxybenzoic acid is 9-17: 5-17: 2.5, and the feeding molar ratio of the triethylamine to the diethyl dichlorophosphamide is 1: 1.
2. Toluene is used as a solvent, pyridine is used as an acid-binding agent, and RAFT reagent 3-benzyl sulfanyl thiocarbonyl sulfanyl propionic acid is subjected to amidation reaction and then subjected to esterification reaction with double-terminal hydroxyl polystyrene to obtain the polystyrene macromolecule transfer agent.
Wherein the molar ratio of the 3-benzylsulfanylthiocarbonylsulfanylpropionic acid to the double-terminal hydroxypolystyrene is 1: 1.
3. The PS-b-PMAA is obtained by taking N, N-dimethylformamide DMF as a solvent, azodiisobutyronitrile as an initiator, a polystyrene macromolecular chain transfer agent as a chain transfer agent and methacrylic acid as a monomer.
Wherein the molar ratio of the azodiisobutyronitrile to the polystyrene macromolecular chain transfer agent to the methacrylic acid is 1:3:800, and the molar concentration of the methacrylic acid is 2 mol/L.
4. Tetrahydrofuran is used as solvent, and the reaction type flame retardant is terminated with benzoic acid poly (diethylamino) ethylene phosphate and SOCl2Performing acyl chlorination reaction, and performing esterification reaction with PS-b-PMAA by using toluene as a solvent and pyridine as an acid-binding agent to obtain the degradable flame-retardant polystyrene block copolymer.
Wherein, PS-b-PMAA, poly (diethylamino) ethylene benzoate terminated by reactive flame retardant and SOCl2In a molar ratio of 1:1: 5.
Wherein the photosensitizer is copper stearate; the sun-screening agent is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; the degradation control agent is antioxidant 1010.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a degradable flame-retardant polystyrene block copolymer, which is prepared by block-adding flame retardant macromolecules on a polystyrene molecular chain, so that a polystyrene material has lasting flame-retardant performance.
(2) The invention provides a degradable flame-retardant polystyrene block copolymer, which is characterized in that a photosensitizer, a sun-screening agent and a degradation control agent are added into a block polymethacrylic acid on a polystyrene molecular chain and the polystyrene block copolymer to realize the rapid degradation of the polystyrene block copolymer.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the degradable flame-retardant polystyrene block copolymer prepared in example 8.
FIG. 2 is an infrared spectrum of a degradable flame-retardant polystyrene block copolymer prepared in example 8.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Adding diethyl dichlorophosphamide (10mmol), triethylamine (10mmol) and chloroform with the mass twice that of the diethyl dichlorophosphamide into a three-neck flask provided with a reflux condenser tube, a constant-pressure dropping funnel and a magneton stirring device, fully dissolving and uniformly mixing; weighing ethylene glycol (10mmol), dissolving the ethylene glycol in chloroform with the mass twice, placing the solution into a constant-pressure dropping funnel, removing an ice bath after dripping within 1h in the ice bath, slowly heating the solution to 70 ℃ for refluxing for 6h, injecting a chloroform solution of p-hydroxybenzoic acid (2.5mmol) by using a disposable needle tube, continuing preserving the temperature and refluxing for 3h to finish the reaction, cooling the solution to room temperature, distilling the solution under reduced pressure to remove the solvent, filtering the solution, taking the filtrate, dissolving the filtrate again by using chloroform, extracting the filtrate for 3 times by using distilled water, taking the organic phase, distilling the organic phase under reduced pressure to remove the solvent, and obtaining the reactive flame retardant-terminated benzoic acid poly (diethylamino) ethylene phosphate with the yield of 70.6%.
Example 2
RAFT reagent 3-benzylsulfanylthiocarbonylsulfanylpropionic acid (1.0mmol) and 20ml of anhydrous tetrahydrofuran THF were added to a reactor, and after the reaction temperature had risen to 70 ℃ SOCl was slowly added dropwise2(4.0mmol) and after the dropwise addition, the reaction was carried out for 2 hours, after the completion of the reaction, SOCl was removed by distillation under reduced pressure2And THF to obtain 3-benzylsulfanylthiocarbonyl sulfanylpropionyl chloride, and dissolving in toluene.
Both terminal hydroxy polystyrene (1.0mmol) was charged into a 50ml Schlenk flask, and after purging nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after the hydroxyl polystyrene at the two ends is completely dissolved, the mixture is stirred for 30min, the 3-benzyl sulfanyl thiocarbonyl sulfanyl propionyl chloride is dripped, the temperature is raised to 80 ℃, the reaction is continued for 2.5h, the product is cooled to room temperature, the solution is continuously dissolved/precipitated by toluene/methanol for two times, and the solution is dried to constant weight under vacuum at 45 ℃, so that the polystyrene macromolecule transfer agent is obtained, and the yield is 76.3%.
Example 3
Methacrylic acid (16.0mmol), polystyrene macromolecular chain transfer agent (0.06mmol) and azobisisobutyronitrile (0.02mmol) were added to a 50ml Schlenk flask and after three nitrogen extractions, N was added2Under protection, 20mL of N, N-dimethylformamide DMF is added by a disposable syringe, the mixture reacts for 2h in an oil bath at 70 ℃, the mixture is put into liquid nitrogen to quench the product to stop the reaction, methanol/water is used as a precipitator, the precipitation is repeated for 3 times, and the product is dried to constant weight at the temperature of 45 ℃ in vacuum to obtain PS-b-PMAA with the yield of 71.5 percent.
Example 4
Methacrylic acid (16.0mmol), polystyrene macromolecular chain transfer agent (0.06mmol), azobisisobutyronitrile (0.02mmol) were addedAfter three nitrogen purgations in a 50ml Schlenk flask, N2Under protection, 20mL of N, N-dimethylformamide DMF is added by a disposable syringe, the mixture reacts for 4 hours in an oil bath at 70 ℃, the mixture is put into liquid nitrogen to quench the reaction, methanol/water is used as a precipitator, the precipitation is repeated for 3 times, and the mixture is dried to constant weight at the temperature of 45 ℃ in vacuum to obtain PS-b-PMAA, wherein the yield is 73.2%.
Example 5
Methacrylic acid (16.0mmol), polystyrene macromolecular chain transfer agent (0.06mmol) and azobisisobutyronitrile (0.02mmol) were added to a 50ml Schlenk flask and after three nitrogen extractions, N was added2Under protection, 20mL of N, N-dimethylformamide DMF is added by a disposable syringe, the mixture reacts for 6h under 70 ℃ oil bath, the mixture is put into liquid nitrogen to quench the product to stop the reaction, methanol/water is used as a precipitator, the precipitation is repeated for 3 times, and the product is dried under vacuum at 45 ℃ until the weight is constant, so that PS-b-PMAA is obtained, wherein the yield is 74.6%.
Example 6
Adding poly (diethylamino) ethylene phosphate (4.0mmol) benzoate end of reactive flame retardant and 20ml anhydrous tetrahydrofuran THF, slowly dropwise adding SOCl after reaction temperature rises to 70 DEG C2(6.0mmol) and after the dropwise addition reaction for 2 hours, the reaction was terminated and then SOCl was removed by distillation under reduced pressure2And THF to obtain the reaction type flame retardant terminated benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product.
PS-b-PMAA (40mmol) prepared in example 3 was charged into a 50ml Schlenk flask, and after purging nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after PS-b-PMAA is completely dissolved, the mixture is stirred for 30min, then the reaction type flame retardant end benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product dissolved in the toluene is dripped, the temperature is raised to 80 ℃, the reaction is continued for 2.5h, the product is cooled to room temperature, and after toluene/methanol continuous dissolution/precipitation circulation is carried out twice, the product is dried to constant weight under vacuum at 45 ℃, so that the degradable flame retardant polystyrene block copolymer is obtained, and the yield is 67.4%.
Example 7
Reacting the reaction type flame retardant with poly (diethylamino) ethylene phosphate (4.0 mmo)l) and 20ml of anhydrous tetrahydrofuran THF, after the reaction temperature had risen to 70 ℃ SOCl was slowly added dropwise2(6.0mmol) and after the dropwise addition reaction for 2 hours, the reaction was terminated and then SOCl was removed by distillation under reduced pressure2And THF to obtain the reaction type flame retardant terminated benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product.
PS-b-PMAA (40mmol) prepared in example 4 was charged into a 50ml Schlenk flask, and after purging nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after PS-b-PMAA is completely dissolved, the mixture is stirred for 30min, then the reaction type flame retardant end benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product dissolved in the toluene is dripped, the temperature is raised to 80 ℃, the reaction is continued for 2.5h, the product is cooled to room temperature, and after toluene/methanol continuous dissolution/precipitation circulation is carried out twice, the product is dried to constant weight under vacuum at 45 ℃, so that the degradable flame retardant polystyrene block copolymer is obtained, and the yield is 70.2%.
Example 8
Adding poly (diethylamino) ethylene phosphate (4.0mmol) benzoate end of reactive flame retardant and 20ml anhydrous tetrahydrofuran THF, slowly dropwise adding SOCl after reaction temperature rises to 70 DEG C2(6.0mmol) and after the dropwise addition reaction for 2 hours, the reaction was terminated and then SOCl was removed by distillation under reduced pressure2And THF to obtain the reaction type flame retardant terminated benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product.
PS-b-PMAA (40mmol) prepared in example 5 was charged into a 50ml Schlenk flask, and after purging nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after PS-b-PMAA is completely dissolved, the mixture is stirred for 30min, then the reaction type flame retardant end benzoic acid poly (diethylamino) phosphoric acid ethylene ester acyl chloride product dissolved in the toluene is dripped, the temperature is raised to 80 ℃, the reaction is continued for 2.5h, the product is cooled to room temperature, and after two times of continuous dissolution/precipitation circulation of toluene/methanol, the product is dried to constant weight under vacuum at 45 ℃, so that the degradable flame retardant polystyrene block copolymer is obtained, wherein the yield is 71.6%.
Example 9
Before processing, the degradable flame-retardant polystyrene block copolymer prepared in example 6 is dried in vacuum at 80 ℃ for 12h, 60 parts by mass of the degradable flame-retardant polystyrene block copolymer prepared in example 6, 5 parts by mass of copper stearate, 5 parts by mass of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts by mass of antioxidant 1010 are added to an open mill with a two-roll temperature of 235 ℃, after the mixture is melted and coated on a roll, the mixture is mixed for 10min and then uniformly taken out, the piece is hot-pressed for 10min at 240 ℃ on a flat vulcanizing machine, cold-pressed for 8min at room temperature and taken out, and various standard sample strips are prepared on a universal sampling machine.
Example 10
Before processing, the degradable flame-retardant polystyrene block copolymer prepared in example 7 is dried in vacuum at 80 ℃ for 12h, the degradable flame-retardant polystyrene block copolymer prepared in example 6, 5 parts by mass of copper stearate, 5 parts by mass of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts by mass of antioxidant 1010 are added on an open mill with a two-roll temperature of 235 ℃, after the mixture is melted and coated on a roll, the mixture is mixed for 10min and then uniformly taken out, the mixture is hot-pressed on a flat plate vulcanizing machine at 240 ℃ for 10min, cold-pressed at room temperature for 8min and taken out, and various standard sample strips are prepared on a universal sampling machine.
Example 11
Before processing, the degradable flame-retardant polystyrene block copolymer prepared in example 8 is dried in vacuum at 80 ℃ for 12h, 100 parts by mass of the degradable flame-retardant polystyrene block copolymer prepared in example 6, 5 parts by mass of copper stearate, 5 parts by mass of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts by mass of antioxidant 1010 are added to an open mill with a two-roll temperature of 235 ℃, after the mixture is melted and coated on a roll, the mixture is mixed for 10min and then uniformly taken out, and various standard sample strips are prepared on a universal sampling machine after the mixture is subjected to hot pressing at 240 ℃ for 10min, cold pressing at room temperature for 8min and taken out.
Comparative example 1
Before processing, polystyrene is dried for 12 hours in vacuum at 80 ℃, 100 parts by mass of polystyrene, 5 parts by mass of copper stearate, 5 parts by mass of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts by mass of antioxidant 1010 are added on an open type heat mill with a double-roll temperature of 235 ℃, after the polystyrene, the copper stearate, the 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and the antioxidant 1010 are melted and coated on a roll, the mixture is mixed for 10min and then evenly taken out, the sheet is hot pressed for 10min at 240 ℃ on a flat vulcanizing machine, the room temperature is cold pressed for 8min, the sheet is taken out, and various standard sample strips are prepared on a universal sampling machine.
Limiting oxygen index test: the instrument is FTAII (1600) type limit oxygen index instrument of RS company in UK, test standard GB/T2406.2-2009, spline specification 100mm x 6mm x 3mm, and a group of 5-10, before test, the spline is placed in an environment with temperature 23 + -2 deg.C and humidity 50 + -5% and adjusted for more than 88 h.
UL-94 vertical burning test: the instrument is an CZF-5A horizontal vertical combustion tester of Jiangning analytical instruments factory for carrying out UL-94 vertical combustion test, the specification of the sample bar is 125mm multiplied by 13mm multiplied by 3.2mm, and the test standard is UL94ISBN 0-7629 and 0082-2. Before testing, the sample is put in an environment with the temperature of 23 +/-2 ℃ and the humidity of 50 +/-5% and is adjusted for more than 48 h.
Table 1 shows the flame retardant properties and the degradability of the degradable flame retardant polystyrene block copolymer.
| Sample (I) | LOI(％) | UL-94 | Degradation rate (%) for 6 days under the conditions of the buried test |
| Example 9 | 37.2 | V-1 | 26.1 |
| Example 10 | 35.6 | V-1 | 24.5 |
| Example 11 | 34.1 | V-1 | 21.7 |
| Comparative example 1 | 18.3 | N.R | 12.1 |
As can be seen from Table 1, the flame retardant property of polystyrene can be significantly improved by the present invention wherein the flame retardant macromolecule is blocked on the polystyrene polymer chain. As can be seen from the comparison of the data of example 9, example 10, example 11 and comparative example 1, the LOI of pure PS is only 18.3%, and when the polystyrene is modified by blocking the macromolecule with flame retardance on the polystyrene polymer chain, the LOI can reach 37.2%, which effectively improves the flame retardant property of the polystyrene.
As can be seen from fig. 1 and fig. 2, the degradable performance of the degradable flame-retardant polystyrene block copolymer material prepared in example 11 is more excellent, and the possible reason is that the degradable performance of the polymer material is improved due to the interaction between the polymethacrylic acid on the molecular chain of the degradable flame-retardant polystyrene block copolymer and the added antioxidant, and when the molecular weight of the polymethacrylic acid on the molecular chain is larger, the degradable performance of the polymer material is better.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The degradable flame-retardant polystyrene block copolymer material is characterized by consisting of 60-100 parts by mass of degradable flame-retardant polystyrene block copolymer, 5 parts by mass of photosensitizer, 5 parts by mass of sun-screening agent and 5 parts by mass of degradation control agent, wherein the degradable flame-retardant polystyrene block copolymer has a structure shown in a formula (I):
in the formula, n is 15-30, m is 7-15, and P is 10-20.
2. The degradable flame-retardant polystyrene block copolymer material of claim 1, wherein the photosensitizer is copper stearate.
3. The degradable flame-retardant polystyrene block copolymer material of claim 1, wherein the sun-blocking agent is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
4. The degradable flame-retardant polystyrene block copolymer material of claim 1, wherein the degradation control agent is antioxidant 1010.
5. The degradable flame-retardant polystyrene block copolymer material of claim 1, comprising the steps of:
vacuum drying the degradable flame-retardant polystyrene block copolymer at 80 ℃, adding 60-100 parts by mass of the degradable flame-retardant polystyrene block copolymer, 5 parts by mass of a photosensitizer, 5 parts by mass of a sun-screening agent and 5 parts by mass of a degradation control agent into an open type heat mill with a double-roller temperature of 235 ℃, uniformly mixing and discharging the materials after the materials are melted and coated on rollers, and carrying out hot pressing, cold pressing at room temperature and discharging on a flat vulcanizing machine at 240 ℃ to obtain the degradable flame-retardant polystyrene block copolymer material.
6. The method for preparing the degradable flame-retardant polystyrene block copolymer according to claim 1, comprising the steps of:
(1) taking triethylamine as a catalyst and an acid-binding agent, chloroform as a reaction solvent, reacting diethyl dichlorophosphamide with ethylene glycol at 60-70 ℃ for 4-6 h, continuously adding p-hydroxybenzoic acid for end capping, carrying out heat preservation and reflux for 2-3 h to finish the reaction, and carrying out reduced pressure distillation, suction filtration and extraction on the crude product to obtain reaction type flame retardant terminal benzoic acid poly (diethylamino) ethylene phosphate;
(2) carrying out amidation reaction on toluene serving as a solvent, pyridine serving as an acid-binding agent and RAFT reagent 3-benzylsulfanylthiocarbonyl sulfanylpropionic acid, and then carrying out esterification reaction on the amidation reaction product and double-terminal hydroxy polystyrene to obtain a polystyrene macromolecule transfer agent;
(3) taking N, N-dimethylformamide DMF as a solvent, azodiisobutyronitrile as an initiator, a polystyrene macromolecular chain transfer agent as a chain transfer agent, and methacrylic acid as a monomer to obtain PS-b-PMAA;
(4) tetrahydrofuran is used as solvent, and the reaction type flame retardant is terminated with benzoic acid poly (diethylamino) ethylene phosphate and SOCl2Performing acyl chlorination reaction, and performing esterification reaction with PS-b-PMAA by using toluene as a solvent and pyridine as an acid-binding agent to obtain the degradable flame-retardant polystyrene block copolymer.
7. The method for preparing the degradable flame-retardant polystyrene block copolymer according to claim 2, wherein in the step (1), the feeding molar ratio of the diethyl dichlorophosphine amide, the ethylene glycol and the p-hydroxybenzoic acid is 9-17: 5-17: 2.5, and the feeding molar ratio of the triethylamine and the diethyl dichlorophosphine amide is 1: 1.
8. The method for preparing the degradable flame-retardant polystyrene block copolymer according to claim 2, wherein in the step (2), the molar ratio of the 3-benzylsulfanylthiocarbonylsulfanylpropionic acid to the both-terminal hydroxystyrene is 1: 1.
9. The method for preparing the degradable flame-retardant polystyrene block copolymer according to claim 2, wherein in the step (3), the molar ratio of the azobisisobutyronitrile to the polystyrene macromolecular chain transfer agent to the methacrylic acid is 1:3:800, and the molar concentration of the methacrylic acid is 2 mol/L.
10. The method for preparing the degradable flame-retardant polystyrene block copolymer according to claim 2, wherein in the step (4), the PS-b-PMAA, the poly (diethylamino) ethylene phosphate benzoate terminated with the reactive flame retardant, and SOCl are added2In a molar ratio of 1:1: 5.
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