CN115044140B - Preparation process of environment-friendly flame-retardant polystyrene material - Google Patents
Preparation process of environment-friendly flame-retardant polystyrene material Download PDFInfo
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- CN115044140B CN115044140B CN202210768398.8A CN202210768398A CN115044140B CN 115044140 B CN115044140 B CN 115044140B CN 202210768398 A CN202210768398 A CN 202210768398A CN 115044140 B CN115044140 B CN 115044140B
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- hollow glass
- glass beads
- latex
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- polystyrene material
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 53
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 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 37
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 67
- 239000011324 bead Substances 0.000 claims abstract description 54
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims abstract description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 229920000126 latex Polymers 0.000 claims description 27
- 239000004816 latex Substances 0.000 claims description 27
- 239000004005 microsphere Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 3
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 229920006173 natural rubber latex Polymers 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- -1 polydimethylsiloxane Polymers 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000008719 thickening Effects 0.000 claims description 3
- 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 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 4
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- XQFYGXFPKONEPY-UHFFFAOYSA-N 2,3-diphenylfuran Chemical class O1C=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 XQFYGXFPKONEPY-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical class C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- 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
- C08K7/28—Glass
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation process of an environment-friendly flame-retardant polystyrene material, which is characterized by comprising the following steps of: 1) Modifying hollow glass beads; 2) Wrapping natural latex; 3) Mixing inorganic flame retardants; 4) And (5) extruding and granulating. The invention firstly adopts decabromodiphenyl ethane (DBDPE) flame retardant and Sb 2 O 3 The compounded flame retardant component has good synergistic effect, and the optimal proportion of the two components is selected; in the invention, the brittleness of the PS resin is changed by adding the hollow glass beads, and in order to promote the fusion degree of the PS resin and the hollow glass beads, firstly, carrying out hydrophobic modification on hollow glass beads by adopting a silane coupling agent, then soaking natural latex, and wrapping or filling holes of the hollow glass beads so as to enable the hollow glass beads to carry a large amount of inert gas; the flame retardant property of the PS/hollow glass bead composite material reaches the V0 flame retardant level, and the PS/hollow glass bead composite material has no peculiar smell and is environment-friendly; it has certain transparency, high tensile strength and better flame-extinguishing and flame-retarding effects.
Description
Technical Field
The invention relates to the technical field of modified PS resin, in particular to a preparation process of an environment-friendly flame-retardant polystyrene material.
Background
PS resin itself belongs to inflammable material, limiting oxygen index is 18%, and it is decomposed into secondary products such as styrene monomer after high temperature. Brominated flame retardants commonly used for PS materials are harmful to the environment and human body, and the restrictions of PS materials in the related application fields are gradually increasing.
The common polystyrene resin is nontoxic, odorless and colorless transparent particles, and is similar to glass-like brittle materials, and the product has extremely high transparency, light transmittance reaching more than 90%, good electrical insulation property, easy coloring, good processing fluidity, good rigidity, good chemical corrosion resistance and the like. The method has wide application in the fields of electric appliances such as lamps, screens, electric appliance protection covers and the like.
However, the common polystyrene has the disadvantages of brittleness, low impact strength, easy occurrence of stress cracking, poor heat resistance, poor boiling water resistance and the like. Therefore, in the application field of the electric appliances, the PS resin needs to be added with a flame retardant, and the common polybrominated diphenyl ether flame retardant has an ether bond, so that polybrominated dibenzodioxin and polybrominated diphenyl furan are easy to generate in the combustion process, and pollution is generated.
More importantly, the addition of the flame retardant has a great influence on the PS performance, such as the tensile strength is damaged, so that the amount of the flame retardant component needs to be tested for a plurality of times, and a new reinforcing agent component is needed to be added in the best method. After the invention is fully researched and tested, hollow glass beads are tried to be added into PS resin to strengthen the material strength.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation process of an environment-friendly flame-retardant polystyrene material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation process of the environment-friendly flame-retardant polystyrene material comprises the following steps:
1) Modifying hollow glass beads: selecting hollow glass beads with the outer diameter smaller than 50 mu m and coated with inert gas, and carrying out the following treatment:
(1) firing at high temperature: baking at 350deg.C for 1min, and removing surface sizing agent;
(2) surface modification: soaking in 2% silane coupling agent water solution for 30min, and drying;
2) And (3) wrapping natural rubber latex: taking ammonia-preserved natural latex, adding a glycerol monostearate foaming agent, stirring at a high speed to generate a large amount of bubbles, adding silane-modified hollow glass beads into the latex, dripping a polydimethylsiloxane defoaming agent, and stirring at a low speed for 30min;
heating to 60-70 ℃, rapidly and greatly reducing the viscosity of the latex, and decompressing and removing volatile matters and water in a degassing tank until the solid content reaches 55% +/-5%; continuously stirring at a low speed, naturally cooling to room temperature, gradually thickening the latex viscosity, and suspending the hollow glass microspheres in a system; after standing and ageing for 1-2 days, gradually disappearing bubbles, agglomerating a part of small-particle-size latex into large-particle-size latex, adhering the other part of small-particle-size latex to the surface of suspended hollow glass beads, sucking supernatant for later use, wherein the solid content of the residual latex reaches 65% +/-5%; promoting agglomeration of small-particle-size latex by modifying the hollow glass microspheres;
3) Mixing inorganic flame retardants: taking out the hollow glass beads, N 2 Under the condition, the vibrating screen shakes the screen and washes 3 times through the supernatant; continuing shaking, kneading, adding Sb 2 O 3 A powder; n (N) 2 Blowing and ventilating, and drying in a fluidized bed to obtain the wrapped natural latex and Sb 2 O 3 The floating rate of the hollow glass beads in the test water reaches more than 95%, which indicates that most of the bead holes are blocked;
4) And (3) extruding and granulating: adding the hollow glass beads, PS powder, decabromodiphenyl ethane powder, antioxidant and toner obtained in the step 3), uniformly stirring, and adding into a double-screw extruder for melt extrusion granulation to obtain the finished flame-retardant polystyrene material.
Preferably, in step 1), the hollow glass microspheres are produced by a chemical foaming method or a mechanical foaming method, in particular by 3M company, having a wall thickness of 1-2 μm and containing an inert gas (N) 2 Or CO 2 ) And the hollow glass microsphere with the outer diameter smaller than 50 mu m is obtained through sieving treatment.
Preferably, in step 2), the natural latex is in particular preserved with low ammonia (NH 3 % 0.2%) of low concentration normal latex (T.S% 35-40%).
Preferably, in step 3), the mesh number of the vibrating screen is 600-800 mesh.
Preferably, in step 3), sb 2 O 3 In particular to ultra-micro Sb subjected to ball milling treatment 2 O 3 And (3) powder.
Preferably, in step 4), the antioxidant is specifically compounded from antioxidant 1010 and antioxidant 168.
The final flame-retardant polystyrene material comprises the following components in parts by weight:
PS,100 parts;
9-11 parts of hollow glass beads;
decabromodiphenyl ethane, 17 parts;
Sb 2 O 3 3 parts;
1010,0.1 parts of an antioxidant;
1680.2 parts of an antioxidant;
less than 5 parts of toner;
the balance of residual dosage after drying the silane modifier, the natural latex, the foaming agent and the defoamer.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention firstly adopts decabromodiphenyl ethane (DBDPE) flame retardant and Sb 2 O 3 The compound flame retardant component has the advantages that DBDPE and decabromodiphenyl ether have the same bromine content and similar molecular structure, but different from polybrominated diphenyl ether flame retardants, no ether bond exists in DBDPE molecules, polybrominated dibenzodioxin and polybrominated diphenyl furan are not generated in the combustion process, the flame retardant performance is basically equivalent to that of decabromodiphenyl ether, and the heat resistance, the light resistance, the difficult dialyzability and the like are superior to those of decabromodiphenyl ether. And DBDPE and Sb 2 O 3 Has good synergistic effect.
2. In order to change the brittleness of PS resin, the hollow glass beads are added for reinforcement, and in order to promote the fusion degree of the PS resin and the hollow glass beads, the silane coupling agent is firstly adopted for hydrophobic modification, then natural latex is soaked, holes of the hollow glass beads are wrapped or filled, and a large amount of inert gas is carried by the hollow glass beads, so that the hollow glass beads have the following advantages:
1) The surface emulsion layer promotes the melt mixing uniformity with PS resin and enhances the toughness of the material;
2) The hollow glass beads carry a large number of holes, so that the overall density of the material is reduced (the density is about 1.04), and the lightening is improved;
3) A large amount of inert gas carried in the hollow glass microsphere holes overflows a large amount of inert gas and DBDPE and Sb when the holes are broken by burning and heating (emulsion coating is broken) 2 O 3 SbBr produced by the reaction n The volatile components are together, so that the emptying efficiency during combustion is greatly improved, and the flame-extinguishing and flame-retarding effects are greatly improved.
3. The flame retardant property of the PS/hollow glass bead composite material reaches the V0 flame retardant level, and the PS/hollow glass bead composite material has no peculiar smell and is environment-friendly; through experiments, when the ratio of decabromodiphenyl ethane to antimonous oxide is 17:3, the tensile strength of the material is influenced; after being reinforced by the hollow glass beads, the tensile strength of the material is higher than that of the common PS material.
Drawings
FIG. 1 is a graph showing the results of a test of the effect of different proportions of flame retardants on the thermal stability of a PS/hollow glass microsphere composite material obtained by the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Example 1:
the preparation process of the environment-friendly flame-retardant polystyrene material comprises the following steps:
1) Hollow glass bead modification: selecting hollow glass beads with the outer diameter smaller than 50 mu m and coated with inert gas, and carrying out the following treatment:
(1) firing at high temperature: baking at 350deg.C for 1min, and removing surface sizing agent;
(2) surface modification: soaking in 2% water solution of silane coupling agent for 30min, drying;
2) And (3) wrapping natural rubber latex: taking ammonia-preserved natural latex, adding a glycerol monostearate foaming agent, stirring at a high speed to generate a large amount of bubbles, adding silane-modified hollow glass beads into the latex, dripping a polydimethylsiloxane defoaming agent, and stirring at a low speed for 30min;
heating to 60-70 ℃, rapidly and greatly reducing the viscosity of the latex, and decompressing and removing volatile matters and water in a degassing tank until the solid content reaches 55% +/-5%; continuously stirring at a low speed, naturally cooling to room temperature, gradually thickening the latex viscosity, and suspending the hollow glass microspheres in a system; after standing and ageing for 1-2 days, gradually disappearing bubbles, agglomerating a part of small-particle-size latex into large-particle-size latex, adhering the other part of small-particle-size latex to the surface of suspended hollow glass beads, sucking supernatant for later use, wherein the solid content of the residual latex reaches 65% +/-5%; promoting agglomeration of small-particle-size latex by modifying the hollow glass microspheres;
3) Mixing inorganic flame retardants: taking out the hollow glass beads, N 2 Conditions (conditions)And then the vibrating screen shakes the screen, washing 3 times through supernatant; continuing shaking, kneading, adding Sb 2 O 3 A powder; n (N) 2 Blowing and ventilating, and drying in a fluidized bed to obtain the wrapped natural latex and Sb 2 O 3 The floating rate of the hollow glass beads in the test water reaches more than 95%, which indicates that most of the bead holes are blocked;
4) And (3) extruding and granulating: adding the hollow glass beads, PS powder, decabromodiphenyl ethane powder, antioxidant and toner obtained in the step 3), uniformly stirring, and adding into a double-screw extruder for melt extrusion granulation to obtain the finished flame-retardant polystyrene material.
Example 2:
the impact test of different proportions of flame retardants in the PS/hollow glass bead composite material obtained by the invention on the thermal stability of the material is shown in figure 1. So the optimal proportion of the optimal bi-component flame retardant is finally obtained, and the flame-retardant polystyrene material of the finished product comprises the following components in parts by weight:
PS,100 parts;
9-11 parts of hollow glass beads;
decabromodiphenyl ethane, 17 parts;
Sb 2 O 3 3 parts;
1010,0.1 parts of an antioxidant;
168,0.2 parts of an antioxidant;
less than 5 parts of toner;
the balance of residual dosage after drying the silane modifier, the natural latex, the foaming agent and the defoamer.
Example 3:
hollow glass microsphere treatment and impact test on PS performance, the following test group was selected
Group a test: a general-purpose PS resin material to which the same antioxidant and toner as in example 2 were added;
group b test: the same flame retardant component as in example 2 was continued to be added in the group a test;
group c test: the untreated hollow glass microspheres of the same parts by weight as in example 2 were continuously added in the group b test;
butyl group test: the untreated hollow glass microspheres in the group C test were replaced with the hollow glass microspheres treated in example 1.
The following data were obtained from the respective tests, see table 1 below:
TABLE 1 impact test of flame retardant and hollow glass microbeads on PS Performance
The data show that the fusion degree of the hollow glass beads and PS seriously affects the rigidity and toughness of the composite material, so the invention adopts the silanization surface treatment of the hollow glass beads and the impregnation of natural latex to form a suspended hollow glass bead structure with colloidal particles adhered on the surface; meanwhile, the addition of the modified hollow glass beads greatly promotes the agglomeration efficiency of the natural latex;
the inorganic flame retardant is adhered outside the hollow glass, so that hollow glass beads with high floating rate and a large amount of inert gas carried in holes are obtained, on one hand, the melt mixing uniformity of the hollow glass beads and a PS phase is promoted, and a uniform phase is formed, so that enough transparency is ensured, and the application range is wider; on the other hand, when the burning and heating holes (broken latex coating), a large amount of inert gas overflows, and DBDPE and Sb are mixed 2 O 3 SbBr produced by the reaction n The volatile components are together, so that the emptying efficiency during combustion is greatly improved, and the flame-extinguishing and flame-retarding effects are greatly improved. Finally, the high-performance modified PS resin material with enhanced rigidity and toughness, halogen-free flame retardance reaching V0 level is obtained, and the service life and the flame-retardant and heat-resistant service performance of the high-performance modified PS resin material are greatly enhanced.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The preparation process of the environment-friendly flame-retardant polystyrene material is characterized by comprising the following steps of:
1) Modifying hollow glass beads: selecting hollow glass beads with the outer diameter smaller than 50 mu m and coated with inert gas, and carrying out the following treatment:
(1) firing at high temperature: baking at 350deg.C for 1min, and removing surface sizing agent;
(2) surface modification: soaking in 2% silane coupling agent water solution for 30min, and drying;
2) And (3) wrapping natural rubber latex: taking ammonia-preserved natural latex, adding a glycerol monostearate foaming agent, stirring at a high speed to generate a large amount of bubbles, adding silane-modified hollow glass beads into the latex, dripping a polydimethylsiloxane defoaming agent, and stirring at a low speed for 30min;
heating to 60-70 ℃, rapidly and greatly reducing the viscosity of the latex, and decompressing and removing volatile matters and water in a degassing tank until the solid content reaches 55% +/-5%; continuously stirring at a low speed, naturally cooling to room temperature, gradually thickening the latex viscosity, and suspending the hollow glass microspheres in a system; after standing and ageing for 1-2 days, gradually disappearing bubbles, agglomerating a part of small-particle-size latex into large-particle-size latex, adhering the other part of small-particle-size latex to the surface of suspended hollow glass beads, sucking supernatant for later use, wherein the solid content of the residual latex reaches 65% +/-5%; promoting agglomeration of small-particle-size latex by modifying the hollow glass microspheres;
3) Mixing inorganic flame retardants: taking out the hollow glass beads, N 2 Under the condition, the vibrating screen shakes the screen and washes 3 times through the supernatant; continuing shaking, kneading, adding Sb 2 O 3 A powder; n (N) 2 Blowing and ventilating, and drying in a fluidized bed to obtain the wrapped natural latex and Sb 2 O 3 The floating rate of the hollow glass beads in the test water reaches more than 95%, which indicates that most of the bead holes are blocked;
4) And (3) extruding and granulating: adding the hollow glass beads, PS powder, decabromodiphenyl ethane powder, antioxidant and toner obtained in the step 3), uniformly stirring, and adding into a double-screw extruder for melt extrusion granulation to obtain the finished flame-retardant polystyrene material.
2. The process for preparing the environment-friendly flame-retardant polystyrene material according to claim 1, wherein in the step 1), the hollow glass beads are specifically hollow glass beads which are produced by a 3M company through a chemical foaming method or a mechanical foaming method, have a wall thickness of 1-2 μm, contain inert gas inside and are obtained through sieving treatment, and have an outer diameter of less than 50 μm.
3. The process for preparing environment-friendly flame-retardant polystyrene material according to claim 1, wherein in said step 2), the natural latex is a low-concentration normal latex stored with low ammonia.
4. The process for preparing environment-friendly flame-retardant polystyrene material according to claim 1, wherein in the step 3), the mesh number of the vibrating screen is 600-800 mesh.
5. The process for preparing environment-friendly flame-retardant polystyrene material according to claim 1, wherein in said step 3), said Sb 2 O 3 In particular to ultra-micro Sb subjected to ball milling treatment 2 O 3 And (3) powder.
6. The process for preparing environment-friendly flame-retardant polystyrene material according to claim 1, wherein in the step 4), the antioxidant is specifically compounded from antioxidant 1010 and antioxidant 168.
7. The process for preparing the environment-friendly flame-retardant polystyrene material according to claim 1, wherein the flame-retardant polystyrene material of the finished product obtained in the step 4) comprises the following components in parts by weight:
PS,100 parts;
9-11 parts of hollow glass beads;
decabromodiphenyl ethane, 17 parts;
Sb 2 O 3 3 parts;
1010,0.1 parts of an antioxidant;
1680.2 parts of an antioxidant;
less than 5 parts of toner;
the balance of residual dosage after drying the silane modifier, the natural latex, the foaming agent and the defoamer.
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