CN112662110A - High-toughness flame-retardant PS micro-foaming material - Google Patents
High-toughness flame-retardant PS micro-foaming material Download PDFInfo
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- CN112662110A CN112662110A CN202011514907.1A CN202011514907A CN112662110A CN 112662110 A CN112662110 A CN 112662110A CN 202011514907 A CN202011514907 A CN 202011514907A CN 112662110 A CN112662110 A CN 112662110A
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- 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 55
- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000005187 foaming Methods 0.000 title claims abstract description 28
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 23
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 20
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000004793 Polystyrene Substances 0.000 claims description 36
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920005669 high impact polystyrene Polymers 0.000 claims description 9
- 239000004797 high-impact polystyrene Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 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 description 6
- 239000012745 toughening agent Substances 0.000 claims description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 150000004645 aluminates Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229940075397 calomel Drugs 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000012170 montan wax Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004088 foaming agent Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- 239000013585 weight reducing agent Substances 0.000 abstract description 3
- 239000004594 Masterbatch (MB) Substances 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000001629 suppression Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 30
- 238000009775 high-speed stirring Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
A high-toughness flame-retardant PS micro-foaming material comprises the following substances in parts by weight: 55-70 parts of carrier, 5-10 parts of flexibilizer, 10-20 parts of flame retardant, 10-20 parts of hydrotalcite, 3-8 parts of zinc oxide, 0.5-1 part of activating agent, 1 part of dispersing agent, 0.5 part of antioxidant, 0.1-0.5 part of coupling agent, 0.1 part of cross-linking agent and 0.1-0.3 part of anti-dripping agent. According to the invention, hydrotalcite is added in the process of preparing the PS master batch, and the hydrotalcite has a flame retardant effect, so that the addition amount of the flame retardant can be reduced, and a good flame retardant effect can be achieved under the condition of less flame retardant; meanwhile, the hydrotalcite is decomposed to generate carbon dioxide and water, so that the smoke suppression effect is achieved; and the hydrotalcite is decomposed to generate carbon dioxide, so that the material has a micro-foaming effect without adding a foaming agent, and the weight reduction effect is achieved.
Description
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to a high-toughness flame-retardant PS micro-foaming material.
Background
The PS is inflammable, drops are accompanied during combustion, and simultaneously, a large amount of black smoke exists, so that the application of the PS is limited, therefore, the flame retardant treatment of the PS is a premise of wide application of the PS, but the toughness of the PS material is sharply reduced due to the addition of the inorganic flame retardant, and the applicable range of the PS raw material is greatly reduced. The PS foaming material has wide application, and the PS foaming material in the prior art is mostly foamed by adding a foaming agent or an inflation body. The invention aims to provide a material which is not added with a traditional foaming agent, can ensure that the material performance is basically unchanged and has micro-foaming under the condition of good flame-retardant effect. The micro-foaming toughening flame-retardant material can eliminate shrinkage marks of the product during injection molding, and the appearance of the product is not affected; the bending or deformation of the product caused by internal stress and shrinkage after injection molding is reduced; the pressure maintaining time during injection molding can be reduced, the injection molding period is shortened, and the production efficiency is improved; the foamed product can reduce the weight by 10-15% (depending on the thickness of the product), which is beneficial to reducing the cost of raw materials, and meanwhile, the addition of the flame retardant greatly expands the application range of the material on electric products. The micro-foaming toughening flame retardant material is suitable for products such as automobile components, household products, electric appliance shells and the like.
Disclosure of Invention
The invention provides a high-toughness flame-retardant PS micro-foaming material, which is used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
a high-toughness flame-retardant PS micro-foaming material comprises the following substances in parts by weight: 55-70 parts of carrier, 5-10 parts of flexibilizer, 10-20 parts of flame retardant, 10-20 parts of hydrotalcite, 3-8 parts of zinc oxide, 0.5-1 part of activating agent, 1 part of dispersing agent, 0.5 part of antioxidant, 0.1-0.5 part of coupling agent, 0.1 part of cross-linking agent and 0.1-0.3 part of anti-dripping agent.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the carrier is HIPS (high impact polystyrene).
The high-toughness flame-retardant PS micro-foaming material is characterized in that the toughening agent is a mixture of any one or two of K resin and SBS mixed in any proportion.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the hydrotalcite is calomel hydrotalcite.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the flame retardant is added with an anti-dripping agent for synergistic use.
The high-toughness flame-retardant PS micro-foaming material comprises a flame retardant, wherein the flame retardant comprises decabromodiphenyl ethane and antimony trioxide, and the mass ratio of the decabromodiphenyl ethane to the antimony trioxide is 3.5: 1.
the high-toughness flame-retardant PS micro-foaming material is characterized in that the anti-dripping agent is polytetrafluoroethylene.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the activating agent is sodium stearate.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the dispersing agent is any one of stearic acid, montan wax and amide wax.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the antioxidant is DLTDP.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the coupling agent is an aluminate coupling agent.
The high-toughness flame-retardant PS micro-foaming material is characterized in that the crosslinking agent is a mixture of any one or two of peroxide crosslinking agent DCP (dicumyl peroxide) or BIBP (1, 4-di-tert-butylperoxyisopropyl benzene) in any proportion.
The preparation method of the high-toughness flame-retardant PS micro-foaming material comprises the following steps: accurately weighing the raw materials, pouring the hydrotalcite and the activating agent into a constant-temperature water bath (constant temperature 80-85 ℃), stirring for 1.5h, filtering, washing, pumping to dry to obtain a filter cake, and adjusting the pH value to 7-8 for later use; adding zinc oxide into a high-speed stirring pot, stirring at high frequency for 2min, adding 1/3 coupling agent into a feeding port of the high-speed stirring pot while stirring at low frequency, and stirring at high speed for 8 min; adding HIPS into a high-speed stirring pot, stirring for 2min at high frequency, adding a flame retardant into a feeding hole of the high-speed stirring pot, adding 1/3 coupling agent while stirring at low frequency, and stirring for 8min at high speed; and finally, adding the activated hydrotalcite and the rest materials, stirring for 2min at high frequency, adding the rest 1/3 coupling agent into a feeding port of a high-speed stirring pot while stirring at low frequency, and stirring for 8min at high speed. And (3) extruding and granulating by using a double-screw extruder, wherein the temperature of a first zone to a ninth zone of the extruder is set to be 180-.
The invention has the advantages that: according to the invention, hydrotalcite is added in the process of preparing the PS master batch, and the hydrotalcite has a flame retardant effect, so that the addition amount of the flame retardant can be reduced, and a good flame retardant effect can be achieved under the condition of less flame retardant; meanwhile, the hydrotalcite is decomposed to generate carbon dioxide and water, so that the smoke suppression effect is achieved; and the hydrotalcite is decomposed to generate carbon dioxide, so that the material has a micro-foaming effect without adding a foaming agent, and the weight reduction effect is achieved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an electron micrograph of example 1 of the present invention;
FIG. 2 is an electron micrograph of a comparative example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: 59kg of HIPS, 6kg of K glue, 15kg of hydrotalcite, 0.5kg of an activating agent, 10kg of decabromodiphenylethane, 3kg of antimony trioxide, 1kg of magnesium stearate, 0.5kg of an antioxidant, 0.1kg of a crosslinking agent, 5kg of zinc oxide, 0.2kg of a coupling agent and 0.1kg of an anti-dripping agent are weighed according to the following mixture ratio;
step two: pouring the hydrotalcite and the activating agent into a constant-temperature water bath kettle (constant temperature is 80-85 ℃), stirring for 1.5h, filtering, washing, pumping to form a filter cake, and adjusting the pH value to 7-8 for later use; adding zinc oxide into a high-speed stirring pot, stirring at high frequency for 2min, adding 1/3 coupling agent into a feeding port of the high-speed stirring pot while stirring at low frequency, and stirring at high speed for 8 min; adding HIPS into a high-speed stirring pot, stirring for 2min at high frequency, adding a flame retardant into a feeding hole of the high-speed stirring pot, adding 1/3 coupling agent while stirring at low frequency, and stirring for 8min at high speed; and finally, adding the activated hydrotalcite and the rest materials, stirring for 2min at high frequency, adding the rest 1/3 coupling agent into a feeding port of a high-speed stirring pot while stirring at low frequency, and stirring for 8min at high speed. And (3) extruding and granulating by using a double-screw extruder, wherein the temperature of a first zone to a ninth zone of the extruder is set to be 180-.
Example 2
59kg of HIPS, 6kg of K glue, 15kg of hydrotalcite, 0.5kg of an activating agent, 10kg of decabromodiphenylethane, 3kg of antimony trioxide, 1kg of magnesium stearate, 0.5kg of an antioxidant, 0.1kg of a crosslinking agent, 5kg of zinc oxide, 0.2kg of a coupling agent and 0.1kg of an anti-dripping agent are weighed according to the following mixture ratio;
step two: pouring the hydrotalcite and the activating agent into a constant-temperature water bath kettle (constant temperature is 80-85 ℃), stirring for 1.5h, filtering, washing, pumping to form a filter cake, and adjusting the pH value to 7-8 for later use; adding zinc oxide into a high-speed stirring pot, stirring at high frequency for 2min, adding 1/3 coupling agent into a feeding port of the high-speed stirring pot while stirring at low frequency, and stirring at high speed for 8 min; adding HIPS into a high-speed stirring pot, stirring for 2min at high frequency, adding a flame retardant into a feeding hole of the high-speed stirring pot, adding 1/3 coupling agent while stirring at low frequency, and stirring for 8min at high speed; and finally, adding the activated hydrotalcite and the rest materials, stirring for 2min at high frequency, adding the rest 1/3 coupling agent into a feeding port of a high-speed stirring pot while stirring at low frequency, and stirring for 8min at high speed. And (3) extruding and granulating by using a double-screw extruder, wherein the temperature of a first zone to a ninth zone of the extruder is set to be 180-.
The high-toughness flame-retardant PS micro-foaming material obtained in the example 1-2 is injected into a test strip, and the HIPS material is directly injected into the test strip as a comparison example for performance detection, wherein the detection results are shown in the table I.
Watch 1
The data in the table show that the notch impact performance of the embodiment 1 added with the toughening agent is better than that of the embodiment 2, the specific weight of the embodiments 1 and 2 is lighter than that of the comparative example, and the toughening agent has good flame retardant effect, so that the specific gravity can be reduced on the premise of not adding a foaming agent while the flame retardant effect is ensured, the weight reduction effect is achieved, and the wide popularization and application are facilitated.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A high-toughness flame-retardant PS micro-foaming material is characterized in that: the composition comprises the following substances in parts by weight:
55-70 parts of carrier, 5-10 parts of flexibilizer, 10-20 parts of flame retardant, 10-20 parts of hydrotalcite, 3-8 parts of zinc oxide, 0.5-1 part of activating agent, 1 part of dispersing agent, 0.5 part of antioxidant, 0.1-0.5 part of coupling agent, 0.1 part of cross-linking agent and 0.1-0.3 part of anti-dripping agent.
2. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the carrier is HIPS.
3. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the toughening agent is a mixture of any one or two of K resin and SBS mixed in any proportion.
4. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the hydrotalcite is calomel hydrotalcite.
5. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein:
the flame retardant is added with an anti-dripping agent for synergistic use;
the flame retardant comprises decabromodiphenylethane and antimony trioxide, wherein the mass ratio of the decabromodiphenylethane to the antimony trioxide is 3.5: 1.
the anti-dripping agent is polytetrafluoroethylene.
6. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the activating agent is sodium stearate.
7. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the dispersing agent is any one of stearic acid, montan wax and amide wax.
8. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the antioxidant is DLTDP.
9. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the coupling agent is an aluminate coupling agent.
10. The high-toughness flame-retardant PS micro-foamed material according to claim 1, wherein: the crosslinking agent is any one or a mixture of two of peroxide crosslinking agent DCP or BIBP mixed in any proportion.
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CN104870537A (en) * | 2012-12-19 | 2015-08-26 | 第一工业制药株式会社 | Flame-retardant foamed styrene resin composition |
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