CN114621500A - Composite flame retardant, flame-retardant high impact polystyrene material and preparation method - Google Patents
Composite flame retardant, flame-retardant high impact polystyrene material and preparation method Download PDFInfo
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- CN114621500A CN114621500A CN202210329261.2A CN202210329261A CN114621500A CN 114621500 A CN114621500 A CN 114621500A CN 202210329261 A CN202210329261 A CN 202210329261A CN 114621500 A CN114621500 A CN 114621500A
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- flame retardant
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- impact polystyrene
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 127
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 45
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 48
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 30
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical group CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000004793 Polystyrene Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 20
- 229910052794 bromium Inorganic materials 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 16
- 150000001723 carbon free-radicals Chemical group 0.000 description 13
- -1 dimethylphenyl Chemical group 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000000297 inotrophic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to the technical field of flame retardant modification of polystyrene materials, and provides a composite flame retardant, a flame retardant high impact polystyrene material and a preparation method thereof. The preparation method comprises the steps of firstly loading tris (2, 3-dibromopropyl) isocyanurate and paraquat by porous silica, and then coating by polyether sulfone to obtain the composite flame retardant. The composite flame retardant, high impact polystyrene particles and an antioxidant are premixed and then subjected to melt extrusion granulation to obtain the flame-retardant high impact polystyrene material. Compared with the method that the paraquat and the tris (2, 3-dibromopropyl) isocyanurate are directly added into the high impact polystyrene matrix, the composite flame retardant is used for carrying out flame retardant modification on the high impact polystyrene, and the flame retardant effect is obviously improved.
Description
Technical Field
The invention belongs to the technical field of flame-retardant modification of polystyrene materials, and provides a composite flame retardant, a flame-retardant high impact polystyrene material and a preparation method thereof.
Background
High Impact Polystyrene (HIPS) is a thermoplastic material made from elastomer-modified polystyrene and is a two-phase system consisting of a rubber phase and a continuous polystyrene phase. It has excellent processability, dimensional stability, electrical insulation, impact toughness, rigidity and the like, so that it has wide application in the fields of household appliance shells and parts, packaging containers, building products, instruments and meters and the like.
Like most plastics, high impact polystyrene also has the defect of easy combustion, and the combustion process is accompanied by black smoke, so that the potential safety hazard is large, the application range of the high impact polystyrene is limited, and the flame retardant modification research of the high impact polystyrene is very important. The commonly used flame retardants include chlorine-based flame retardants, bromine-based flame retardants, phosphorus-based flame retardants, intumescent flame retardants, inorganic oxide flame retardants, inorganic hydroxide flame retardants, and the like.
The tris (2, 3-dibromopropyl) isocyanurate is a brominated flame retardant and has the flame retardant effect that: firstly, HBr is generated by cracking, and can capture active free radicals (such as. OH) generated by the combustion chain reaction of the polymer, so that the combustion is inhibited or terminated; secondly, HBr and N generated by cracking2、CO2The gases are not combusted or combustion-supporting, and oxygen in the air can be diluted, so that combustion is inhibited; and thirdly, HBr generated by cracking is an acidic substance, and can promote dehydration and carbonization of the polymer to form a carbonization layer to isolate air and heat. The bromine flame retardant is often combined with the antimony trioxide to realize synergistic flame retardance, and although the addition of the antimony trioxide improves the flame retardant effect and reduces the addition amount of the bromine flame retardant, the antimony trioxide is higher in price and improves the production cost.
Paraquat (2, 3-dimethyl-2, 3-diphenylbutane) is a free radical type flame retardant synergist which, when heated, readily homoscions the C-C bonds between the quaternary carbon atoms to form a dimethylphenyl tertiary carbon radical. The existing research shows that the paraquat can generate synergistic effect on halogen flame retardant, phosphorus flame retardant and the like, and can achieve good flame retardant effect under the condition of adding little or no antimony trioxide. The flame retardant synergistic effect generated by the combination of the paraquat and the bromine flame retardant mainly has two aspects: firstly, dimethyl phenyl tertiary carbon free radical generated by the paraquat cracking can capture active free radical generated by combustion, thereby inhibiting the combustion; and secondly, the dimethyl phenyl tertiary carbon free radical generated by the joint dry cracking can promote the bromine flame retardant to crack to generate HBr, so that the flame retardant effect of the bromine flame retardant is improved.
At present, when the paraquat and the bromine flame retardant are used together, the paraquat and the bromine flame retardant are usually directly added into a polymer matrix according to a certain proportion, so that a good flame retardant effect can be realized, but the flame retardant effect still has a promotion space.
Disclosure of Invention
In order to improve the flame retardant effect of the paraquat and bromine flame retardant on the polymer material, the invention provides a composite flame retardant, a flame-retardant high impact polystyrene material and a preparation method thereof, and compared with the method of directly adding paraquat and tris (2, 3-dibromopropyl) isocyanurate into a high impact polystyrene matrix, the method of the invention can obviously improve the flame retardant effect.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
in one aspect, the invention provides a preparation method of a composite flame retardant, which comprises the following preparation steps:
(1) adding porous silica into a high-speed mixer, heating to 120 ℃, uniformly mixing the tris (2, 3-dibromopropyl) isocyanurate and the paraquat, adding the mixture into the porous silica after heating and melting, stirring and mixing to ensure that the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are fully adsorbed in pores of the porous silica to prepare the silica loaded with the flame retardant; the rotating speed of the stirring and mixing is 200-300r/min, and the time is 20-30 min;
(2) and (2) adding polyether sulfone and a coupling agent into N, N-dimethylacetamide, heating to 40-50 ℃, stirring until the polyether sulfone and the coupling agent are completely dissolved, defoaming in vacuum, and then spraying and depositing on the surface of the flame retardant-loaded silicon dioxide prepared in the step (1) to form a coating layer to prepare the composite flame retardant.
When the paraquat is used as a synergist of the brominated flame retardant, a dimethyl phenyl tertiary carbon free radical generated by thermal cracking of the paraquat is a key for playing a role in flame retardance and synergism, on one hand, the free radical can capture an active free radical generated by combustion by itself, and on the other hand, the free radical can promote the brominated flame retardant to crack to generate HBr. When the temperature reaches 230 ℃, the paraquat starts to crack to generate dimethyl phenyl tertiary carbon free radicals, and the polymer does not start to burn at the temperature, so that a large number of active free radicals are not generated in the system, and therefore, the paraquat cannot effectively play a role in capturing the active free radicals in the process from the temperature of the polymer rising to 230 ℃ to the time before the start of burning. In the process, the paraquat can not contact with the bromine flame retardant to promote the bromine flame retardant to generate HBr, and the dimethyl phenyl tertiary carbon free radical generated by the cracking of the bromine flame retardant can gradually generate disproportionation reaction to be converted into alpha-methyl ethyl benzene and alpha-methyl styrene, so that the flame retardant synergistic effect is lost. Therefore, in order to enhance the flame retardant synergy of the paraquat, we should react the paraquat with the bromine-based flame retardant as much as possible at this stage to promote the formation of HBr. When the paraquat and bromine-based flame retardants are added directly to the polymer, they are dispersed in the polymer and do not sufficiently and well contact with each other, and before the polymer starts to burn, part of the dimethylphenyl tertiary carbon radicals generated by the paraquat contact with the bromine-based flame retardant to promote the production of HBr, and the other part of the dimethylphenyl tertiary carbon radicals undergo a disproportionation reaction to lose the synergy effect.
The invention adsorbs the paraquat and bromine flame retardant in the pores of the porous silicon dioxide, and then the porous silicon dioxide is coated by the polyether sulfone, and the paraquat and bromine flame retardant are not directly dispersed in the polymer matrix and can be fully contacted. The dimethyl phenyl tertiary carbon radical generated by the joint close cracking can sufficiently promote the bromine-based flame retardant to generate HBr at the temperature of 230 ℃ to the temperature before the polymer is combusted. After the polymer begins to burn, the dimethyl phenyl tertiary carbon free radical generated by residual paraquat and HBr generated by the brominated flame retardant capture active free radicals generated by burning together, and a good flame retardant effect is achieved.
The invention adopts tris (2, 3-dibromopropyl) isocyanurate as a brominated flame retardant, under the mechanical force of high-speed stirring and the capillary adsorption effect, the melted tris (2, 3-dibromopropyl) isocyanurate and the paraquat can be adsorbed by the pores of the porous silica, the melting points of the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are both about 100-110 ℃, and the tris (2, 3-dibromopropyl) isocyanurate and the paraquat can be melted or solidified relatively synchronously when being added into a polymer for subsequent processing or meeting the temperature rise in use, thereby preventing the phenomena of uneven mixing and insufficient contact caused by the flowing of one component and the non-flowing of the other component.
After the flame retardant is added into the polymer, because the subsequent processing temperature of the polymer is usually higher than 110 ℃, the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are remelted in the subsequent processing process, the polyether sulfone is used as the coating layer, the melting point of the polyether sulfone reaches about 300 ℃, and the porous silica adsorbing the flame retardant can be well coated in the processing process. Further, adding a coupling agent into the polyether sulfone, wherein the coupling agent is preferably 3-mercaptopropyltriethoxysilane. It is known that silane coupling agents contain organophilic and inotropic ends and improve the interfacial bonding of silica to organic coatings. The invention adopts 3-mercaptopropyltriethoxysilane, the organophilic end of which contains-SH, and the 3-mercaptopropyltriethoxysilane can form hydrogen bonds with polar groups of polyethersulfone, thereby playing a better coupling effect and being beneficial to improving the stability of the polyethersulfone coating layer in the processing process.
Preferably, in the step (1), the mass ratio of the tris (2, 3-dibromopropyl) isocyanurate to the paraquat to the porous silica is 10: 0.4-1.2: 10-20.
Preferably, in the step (2), the mass ratio of the polyether sulfone to the coupling agent to the N, N-dimethylacetamide to the flame retardant-loaded silica is 10-15: 0.1-0.2: 100: 50.
the invention also provides the composite flame retardant prepared by the preparation method. The composite flame retardant is prepared by loading tris (2, 3-dibromopropyl) isocyanurate and paraquat by porous silica and then coating by polyether sulfone. The flame retardant is used for retarding the flame of the polymer, and before the polymer is combusted, the dimethyl phenyl tertiary carbon free radical generated by joint withering cracking is fully contacted with the tris (2, 3-dibromopropyl) isocyanurate to promote the tris (2, 3-dibromopropyl) isocyanurate to be cracked to generate HBr. The porous silica and the polyether sulfone can not react with acidic HBr, and a great amount of HBr is released after the polyether sulfone layer is damaged along with the temperature rise, so that a great amount of active free radicals can be captured in a short time, and an obvious flame retardant effect is achieved.
On the other hand, the invention provides a preparation method of a flame-retardant high impact polystyrene material, which comprises the following steps:
(1) adding high impact polystyrene particles, a composite flame retardant and an antioxidant into a mixer, and mixing for 5-10min at a speed of 80-120r/min to obtain a mixture; the composite flame retardant is prepared by loading tris (2, 3-dibromopropyl) isocyanurate and paraquat by porous silica and then coating by polyether sulfone;
(2) and adding the mixture into a screw extruder, and extruding and granulating to obtain the flame-retardant high impact polystyrene material.
Preferably, in the mixture, the mass ratio of the high impact polystyrene particles to the composite flame retardant to the antioxidant is 100: 5-15: 0.1-0.2.
Preferably, the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 300-350 r/min.
The antioxidant is selected from common plastic antioxidants.
The invention also provides the flame-retardant high impact polystyrene material prepared by the preparation method.
The invention provides a composite flame retardant, a flame-retardant high impact polystyrene material and a preparation method thereof, compared with the prior art, the invention has the outstanding characteristics and excellent effects that: the composite flame retardant is prepared by loading tris (2, 3-dibromopropyl) isocyanurate and paraquat by porous silica and coating the load by polyether sulfone, so that the paraquat can be fully and effectively contacted with a bromine flame retardant, dimethyl phenyl tertiary carbon free radicals generated by the paraquat can be used for more effectively promoting the bromine flame retardant to decompose to generate HBr before combustion at a high temperature and reducing the loss of synergy caused by disproportionation of the dimethyl phenyl tertiary carbon free radicals generated before combustion. Compared with the method that the paraquat and the tris (2, 3-dibromopropyl) isocyanurate are directly added into the high impact polystyrene matrix, the composite flame retardant is used for carrying out flame retardant modification on the high impact polystyrene, and the flame retardant effect is obviously improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding porous silica into a high-speed mixer, heating to 120 ℃, uniformly mixing the tris (2, 3-dibromopropyl) isocyanurate and the paraquat, adding the mixture into the porous silica after heating and melting, stirring and mixing to ensure that the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are fully adsorbed in pores of the porous silica to prepare the silica loaded with the flame retardant; stirring and mixing at a rotation speed of 200r/min for 30 min; the mass ratio of the tris (2, 3-dibromopropyl) isocyanurate to the paraquat to the porous silica is 10: 1.2: 15;
(2) adding polyether sulfone and 3-mercaptopropyltriethoxysilane into N, N-dimethylacetamide, heating to 40 ℃, stirring until the polyether sulfone and the 3-mercaptopropyltriethoxysilane are completely dissolved, defoaming in vacuum, and then spraying and depositing on the surface of the flame retardant-loaded silicon dioxide prepared in the step (1) to form a coating layer to prepare the composite flame retardant; the mass ratio of the polyether sulfone to the 3-mercaptopropyltriethoxysilane to the N, N-dimethylacetamide to the flame retardant-loaded silicon dioxide is 10: 0.1: 100: 50;
(3) adding high impact polystyrene particles, a composite flame retardant and an antioxidant 168 into a mixer, and mixing at 90r/min for 10min to obtain a mixture; adding the mixture into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the mass ratio of the high impact polystyrene particles to the composite flame retardant to the antioxidant 168 is 100: 15: 0.1; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min.
Comparative example 1
Directly adding porous silica, tris (2, 3-dibromopropyl) isocyanurate, paraquat, polyether sulfone, 3-mercaptopropyltriethoxysilane, high impact polystyrene particles and antioxidant 168 into a mixer, mixing at 90r/min for 10min, discharging, adding into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min; the amounts of the respective raw materials were the same as in example 1.
Example 2
(1) Adding porous silica into a high-speed mixer, heating to 120 ℃, uniformly mixing the tris (2, 3-dibromopropyl) isocyanurate and the paraquat, heating to melt, adding the mixture into the porous silica, stirring and mixing to ensure that the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are fully adsorbed in pores of the porous silica to prepare silica loaded with a flame retardant; the stirring and mixing speed is 300r/min, and the time is 20 min; the mass ratio of the tris (2, 3-dibromopropyl) isocyanurate to the paraquat to the porous silica is 10: 0.8: 15;
(2) adding polyether sulfone and 3-mercaptopropyltriethoxysilane into N, N-dimethylacetamide, heating to 50 ℃, stirring until the polyether sulfone and the 3-mercaptopropyltriethoxysilane are completely dissolved, defoaming in vacuum, and then spraying and depositing on the surface of the flame retardant-loaded silicon dioxide prepared in the step (1) to form a coating layer to prepare the composite flame retardant; the mass ratio of the polyether sulfone to the 3-mercaptopropyltriethoxysilane to the N, N-dimethylacetamide to the flame retardant-loaded silicon dioxide is 12: 0.15: 100: 50;
(3) adding high impact polystyrene particles, a composite flame retardant and an antioxidant 168 into a mixer, and mixing for 10min at a speed of 90r/min to obtain a mixture; adding the mixture into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the mass ratio of the high impact polystyrene particles to the composite flame retardant to the antioxidant 168 is 100: 10: 0.1; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min.
Comparative example 2
Directly adding porous silica, tris (2, 3-dibromopropyl) isocyanurate, paraquat, polyether sulfone, 3-mercaptopropyltriethoxysilane, high impact polystyrene particles and antioxidant 168 into a mixer, mixing at 90r/min for 10min, discharging, adding into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min; the amounts of the respective raw materials were the same as in example 2.
Example 3
(1) Adding porous silica into a high-speed mixer, heating to 120 ℃, uniformly mixing the tris (2, 3-dibromopropyl) isocyanurate and the paraquat, adding the mixture into the porous silica after heating and melting, stirring and mixing to ensure that the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are fully adsorbed in pores of the porous silica to prepare the silica loaded with the flame retardant; the stirring and mixing speed is 250r/min, and the time is 25 min; the mass ratio of the tris (2, 3-dibromopropyl) isocyanurate to the paraquat to the porous silica is 10: 0.4: 15;
(2) adding polyether sulfone and 3-mercaptopropyltriethoxysilane into N, N-dimethylacetamide, heating to 45 ℃, stirring until the polyether sulfone and the 3-mercaptopropyltriethoxysilane are completely dissolved, defoaming in vacuum, and then spraying and depositing on the surface of the flame retardant-loaded silicon dioxide prepared in the step (1) to form a coating layer to prepare the composite flame retardant; the mass ratio of the polyether sulfone to the 3-mercaptopropyltriethoxysilane to the N, N-dimethylacetamide to the flame retardant-loaded silicon dioxide is 15: 0.2: 100: 50;
(3) adding high impact polystyrene particles, a composite flame retardant and an antioxidant 168 into a mixer, and mixing for 10min at a speed of 90r/min to obtain a mixture; adding the mixture into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the mass ratio of the high impact polystyrene particles to the composite flame retardant to the antioxidant 168 is 100: 5: 0.1; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min.
Comparative example 3
Directly adding porous silica, tris (2, 3-dibromopropyl) isocyanurate, paraquat, polyether sulfone, 3-mercaptopropyltriethoxysilane, high impact polystyrene particles and antioxidant 168 into a mixer, mixing at 90r/min for 10min, discharging, adding into a screw extruder, and extruding and granulating to obtain the flame-retardant modified high impact polystyrene material; the heating temperature range of the screw extruder is 170-210 ℃, and the screw rotating speed is 350 r/min; the amounts of the respective raw materials were the same as in example 3.
And (3) performance testing: the flame-retardant modified high impact polystyrene materials of the above examples 1 to 3 and comparative examples 1 to 3 were respectively injection-molded into standard sample bars, tested for oxygen index according to GB/T2406-2009, and subjected to vertical burning test according to UL94 standard to obtain flame-retardant grades, as shown in Table 1.
Table 1:
Claims (10)
1. the preparation method of the composite flame retardant is characterized by comprising the following preparation steps of:
(1) adding porous silica into a high-speed mixer, heating to 120 ℃, uniformly mixing the tris (2, 3-dibromopropyl) isocyanurate and the paraquat, adding the mixture into the porous silica after heating and melting, stirring and mixing to ensure that the tris (2, 3-dibromopropyl) isocyanurate and the paraquat are fully adsorbed in pores of the porous silica to prepare the silica loaded with the flame retardant;
(2) and (2) adding polyether sulfone and a coupling agent into N, N-dimethylacetamide, heating to 40-50 ℃, stirring until the polyether sulfone and the coupling agent are completely dissolved, defoaming in vacuum, and then spraying and depositing on the surface of the flame retardant-loaded silicon dioxide prepared in the step (1) to form a coating layer to prepare the composite flame retardant.
2. The method for preparing the composite flame retardant according to claim 1, wherein in the step (1), the rotation speed of the stirring and mixing is 200-300r/min, and the time is 20-30 min.
3. The preparation method of the composite flame retardant of claim 1, wherein the coupling agent is 3-mercaptopropyltriethoxysilane.
4. The method for preparing the composite flame retardant according to claim 1, wherein in the step (1), the mass ratio of the tris (2, 3-dibromopropyl) isocyanurate to the associated paraquat and porous silica is 10: 0.4-1.2: 10-20.
5. The preparation method of the composite flame retardant according to claim 1, wherein in the step (2), the mass ratio of the polyether sulfone to the coupling agent to the N, N-dimethylacetamide to the flame retardant-loaded silica is 10-15: 0.1-0.2: 100: 50.
6. a composite flame retardant prepared by the method of any one of claims 1 to 5.
7. A preparation method of a flame-retardant high impact polystyrene material comprises the following steps:
(1) adding the high impact polystyrene particles, the composite flame retardant and the antioxidant into a mixer, and mixing for 5-10min at a speed of 80-120r/min to obtain a mixture;
(2) adding the mixture into a screw extruder, and extruding and granulating to obtain the flame-retardant high impact polystyrene material;
the method is characterized in that: the composite flame retardant is the composite flame retardant of claim 6.
8. The preparation method of the flame-retardant high impact polystyrene material according to claim 7, wherein the mass ratio of the high impact polystyrene particles, the composite flame retardant and the antioxidant in the mixture is 100: 5-15: 0.1-0.2.
9. The method as claimed in claim 7, wherein the heating temperature of the screw extruder is 170-210 ℃ and the screw rotation speed is 300-350 r/min.
10. A flame-retardant high impact polystyrene material prepared by the preparation method as claimed in any one of claims 7 to 9.
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