CN104327462A - Phosphorus-based synergistically flame-retardant PET/PBS alloy material and preparation method thereof - Google Patents
Phosphorus-based synergistically flame-retardant PET/PBS alloy material and preparation method thereof Download PDFInfo
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- CN104327462A CN104327462A CN201310310102.9A CN201310310102A CN104327462A CN 104327462 A CN104327462 A CN 104327462A CN 201310310102 A CN201310310102 A CN 201310310102A CN 104327462 A CN104327462 A CN 104327462A
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Abstract
The invention discloses a phosphorus-based synergistically flame-retardant PET/PBS alloy material. The material is composed of the following components: 60.0-85.0 wt% of an ABS resin, 15.0-35.0 wt% of a phosphorus-based flame retardant, 0.0-25.0 wt% of a nitrogen-based flame retardant, 0.4-5.0 wt% of montmorillonite, 0.0-10.0 wt% of a silicon-based synergist, 0.5-15.0 wt% of a compatibilizer and 0.6-0.8 wt% of an antioxidant. According to the invention, the phosphorus-based flame retardant and the nitrogen-based or silicon-based synergist are co-used, montmorillonite is added for synergistic flame retardance, and a preparation method that employs melt blending extrusion is adopted, so that flame-retardant efficiency can be increased; mechanical, processing and other physical properties of halogen-free flame retardant ABS composite material are increased; the amount of toxic gas released during a combustion process can be reduced; and the phosphorus-based synergistically flame-retardant PET/PBS alloy material has low smoke and low toxicity and is an environment-friendly flame-retardant material.
Description
Technical field
The present invention relates to a kind of phosphorus system synergistic Flame-retardant PET/ABS alloy material.
Background technology
PET is polyethylene terephthalate, there is excellent physical and mechanical properties in wide temperature range, life-time service temperature can reach 120 DEG C, electrical insulating property is excellent, and even under high-temperature high-frequency, its electrical property is still better, but corona resistance is poor, creep resistance, resistance to fatigue, rub resistance, dimensional stability are all fine.PET has ester bond, can decompose under strong acid, highly basic and water vapor acting, organic solvent-resistant, good weatherability.Shortcoming is that crystallization rate is slow, and forming process difficulty, molding temperature is high, and the production cycle is long, and impact property is poor.Generally improve its processibility and physical property by methods such as strengthening, fill, be blended, obvious with glass fiber-reinforcing effect, improve resin rigidity, thermotolerance, resistance to chemical reagents, electric property and weathering resistance.But still the slow disadvantage of crystallization velocity need be improved, can take to add the means such as nucleator and crystallization promoter.Add fire retardant and anti-flaming dripping agent can improve PET flame retardant resistance and self-extinguishing.For improving PET performance, PET can form alloy with PC, elastomerics, PBT, PS class, ABS, PA.
ABS is the blend of acrylonitrile-butadiene-styrene copolymer or vinyl cyanide/cinnamic multipolymer and styrene/butadiene copolymers, English name is Acrylonitrile-Butadiene-Styrene (ABS), it is the graft copolymer of divinyl and the mixture of acrylonitritrile-styrene resin, wherein vinyl cyanide accounts for 15%-35%, divinyl accounts for 5%-30%, and vinylbenzene accounts for 40-60%.Along with the change of three kinds of component proportionss, the performance that the physical and mechanical properties of PET/ABS resin changes thereupon is between general-purpose plastics and engineering plastics, and its shock resistance is good, mobility is excellent, but its thermotolerance and weathering resistance poor, mechanical property is not ideal enough, therefore causes its application limited.
PET/ABS alloy is a kind of heterogeneous heterogeneous system, combines the advantage of ABS and PET, has possessed on the one hand shock resistance and the tensile property of ABS, adds the weathering resistance of ABS and chemical resistant properties and glossiness on the other hand.But PET/ABS is typical not compatibilization system, and correspond to ABS or PBT (polybutylene terephthalate), PET price is much lower, and the development potentiality of PET/ABS alloy is huge.
Summary of the invention
The object of the invention is for the low shortcoming of the flame retarding efficiency of halogen-free flame retardants to PET/ABS alloy, a kind of phosphorus system synergistic halogen-free flameproof PET/ABS alloy material is provided, the Flame-retardant PET provided in the present invention/ABS alloy material adopts phosphorus system and nitrogenated flame retardant or phosphorus flame retardant and silicon system synergist is collaborative uses, and can improve the flame retarding efficiency etc. of halogen-free flameproof PET/ABS alloy material; And the poisonous gas discharged in minimizing combustion processes, the few poison of low cigarette.Therefore the phosphorus system synergistic Flame-retardant PET/ABS alloy material in the present invention is a kind of environmentally friendly fire retardant material.
A kind of phosphorus system synergistic Flame-retardant PET/ABS alloy material, this material is made up of following component:
PET/ABS alloy 40.0-80.0 wt%
Phosphorus flame retardant 15.0-25.0wt%
Nitrogenated flame retardant 0.0-20.0wt%
Silicon system synergist 0.0-10.0wt%
Expanding material 0.7-10.0wt%
Toughner 5.0-15.0wt%
Oxidation inhibitor 0.1-1.0wt%
Above component is all weight percentage, the wherein preferred 55.0-75.0wt% of PET/ABS alloy, the preferred 15.0-20.0wt% of phosphorus flame retardant, the preferred 0.0-17.0wt% of nitrogenated flame retardant, the preferred 2.0-8.0wt% of silicon-series five-retardant, the preferred 1.2-8.5wt% of expanding material, the preferred 6.5-13.5wt% of toughner, the preferred 0.35-0.75wt% of oxidation inhibitor.
Described phosphorus flame retardant comprise in pyrophosphate salt, poly-phosphate, organic hypophosphite, inorganic hypophosphite and phosphoric acid salt one or more.
Described nitrogenated flame retardant comprise in trimeric cyanamide, Dyhard RU 100, melamine salt, melamine and salt thereof and guanidinesalt one or more.
Described silicon system synergist comprise in silane, silicone resin, dimethyl siloxane, methylphenyl siloxane, polysilsesquioxane (POSS) one or more.
Described expanding material comprise in methacrylic ester-styrene-butadiene rubber(SBR)-styrol copolymer, methacrylate acrylate-styrol copolymer, acrylate-glycidyl ester-ethene, maleic anhydride stem grafting polyolefin elastomerics, ethylene-acrylate copolymer, ethylene vinyl acetate and acrylonitrile ethylene styrene copolymer one or more.
One or more in described toughner comprises alkylmethacrylate polymer, acryl-butadiene-styrol copolymer, rubber content are 55 ~ 65% acrylonitrile-butadiene-phenylethene grafted copolymer, chlorinatedpolyethylene and ethylacrylate copolymer.
The preparation method of described a kind of phosphorus system synergistic Flame-retardant PET/ABS alloy material is the method adopting melt blending to extrude, concrete technological process and blending condition as follows:
(1) dried fire retardant, synergist, expanding material, toughner, oxidation inhibitor are mixed built agent as fire retardant by proportioning in high-speed mixer.
(2) by the built agent of PC/ABS alloy and fire retardant, join melt blending in twin screw extruder and extrude, the temperature that twin screw extruder is each section is 190-235 DEG C, melt extrudes rear tie rod cooling and dicing.
Embodiment
By the following examples the present invention is specifically described; it is important to point out that following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the person skilled in the art in this field makes the present invention according to the invention described above content, still belong to scope.
embodiment 1
20.0wt% pyrophosphate salt, 10.0 wt% Dyhard RU 100s, 1.0wt% methylphenyl siloxane, 8.0wt% ethylene-acrylate copolymer, 0.6% oxidation inhibitor (0.3wt%1010 and 0.3wt%168) are put into pulverizer and mixed rear obtained composite flame-proof modifier, then after mixing with 60.0wt%ABS, put into twin screw extruder, melt extrude in 190-235 DEG C, and cooling granulation.The LOI of the ABS material of the polynite cooperative flame retardant of gained is 27.2%, UL94 vertical combustion rank is V-0.
embodiment 2
By 18.0wt% hypo-aluminum orthophosphate, 8.0wt% silicone resin, 0.75wt% methacrylic ester-styrene-butadiene rubber(SBR)-styrol copolymer, 0.75wt% oxidation inhibitor (0.3wt%1010 and 0.45wt%168) puts into pulverizer and pulverizes flame-proof modifier obtained composite evenly, then after mixing with 72.0wt%ABS, put into twin screw extruder, melt extrude at 195-220 DEG C, and cooling granulation.The LOI of the ABS material of the polynite cooperative flame retardant of gained is 27.0%, UL94 vertical combustion rank is V-0.
embodiment 3
15.0wt% diethyl hypo-aluminum orthophosphate, 15.0wt% cyanogen urea acid melamine salt, 1.2wt% ethylene-methyl acrylate-glycidyl methacrylate copolymer, 0.8% oxidation inhibitor are put into pulverizer and mixed rear obtained composite flame-proof modifier, then after mixing with the ABS of 63.0wt%, put into twin screw extruder, melt extrude in 200-235 DEG C, and cooling granulation.The LOI of the ABS material of the polynite cooperative flame retardant of gained is 26.8%, UL94 vertical combustion rank is V-0.
Phosphorus system synergistic Flame-retardant PET/ABS alloy material prepared by the embodiment of the present invention is injection molded into the standard batten of test by standard size, its physicals is respectively by China's national standard and U.S. UL standard testing.Wherein ABS resin is German BASF GP22.In various embodiments of the present invention, the corresponding physicals of phosphorus system synergistic Flame-retardant PET/ABS alloy material is in table 1.
Tensile strength GB1040
Elongation at break GB1040
Izod notched Izod impact strength GB1843
Flexural strength GB9341
Incendivity UL94
LOI GB/T 2406-93 PET/ABS alloy 40.0-80.0 wt%
Phosphorus flame retardant 15.0-25.0wt%
Nitrogenated flame retardant 0.0-20.0wt%
Silicon system synergist 0.0-10.0wt%
Expanding material 0.7-10.0wt%
Toughner 5.0-15.0wt%
Oxidation inhibitor 0.1-1.0wt%
Above component is all weight percentage, the wherein preferred 55.0-75.0wt% of PET/ABS alloy, the preferred 15.0-20.0wt% of phosphorus flame retardant, the preferred 0.0-17.0wt% of nitrogenated flame retardant, the preferred 2.0-8.0wt% of silicon-series five-retardant, the preferred 1.2-8.5wt% of expanding material, the preferred 6.5-13.5wt% of toughner, the preferred 0.35-0.75wt% of oxidation inhibitor.
the mechanical property of table 1 embodiment flame-proof ABS and flame retardant properties
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Tensile strength/MPa | 41.2 | 39.4 | 38.9 |
| Tensile modulus/GPa | 2.20 | 2.45 | 2.41 |
| Elongation/% | 6 | 6 | 5 |
| Notched Izod impact strength/KJ/m 2 | 4.4 | 4.3 | 4.2 |
| Flexural strength/MPa | 62.4 | 61.9 | 60.8 |
| Modulus in flexure/GPa | 4.15 | 4.35 | 4.23 |
| Flame retardant rating/3.2mm | V-0 | V-0 | V-0 |
| Oxygen index (LOI)/% | 27.2 | 27.0 | 26.8 |
Claims (7)
1. phosphorus system synergistic Flame-retardant PET/ABS alloy material, is characterized in that, this material is made up of following component:
PET/ABS alloy 40.0-80.0 wt%
Phosphorus flame retardant 15.0-25.0wt%
Nitrogenated flame retardant 0.0-20.0wt%
Silicon system synergist 0.0-10.0wt%
Expanding material 0.7-10.0wt%
Toughner 5.0-15.0wt%
Oxidation inhibitor 0.1-1.0wt%
Above component is all weight percentage, the wherein preferred 55.0-75.0wt% of PET/ABS alloy, the preferred 15.0-20.0wt% of phosphorus flame retardant, the preferred 0.0-17.0wt% of nitrogenated flame retardant, the preferred 2.0-8.0wt% of silicon-series five-retardant, the preferred 1.2-8.5wt% of expanding material, the preferred 6.5-13.5wt% of toughner, the preferred 0.35-0.75wt% of oxidation inhibitor.
2. a kind of phosphorus system according to claim 1 synergistic Flame-retardant PET/ABS alloy material, is characterized in that, described phosphorus flame retardant comprise in pyrophosphate salt, poly-phosphate, organic hypophosphite, inorganic hypophosphite and phosphoric acid salt one or more.
3. a kind of phosphorus system according to claim 2 synergistic Flame-retardant PET/ABS alloy material, is characterized in that, described nitrogenated flame retardant comprise in trimeric cyanamide, Dyhard RU 100, melamine salt, melamine and salt thereof and guanidinesalt one or more.
4. a kind of phosphorus system according to claim 3 synergistic Flame-retardant PET/ABS alloy material, it is characterized in that, described silicon system synergist comprise in silane, silicone resin, dimethyl siloxane, methylphenyl siloxane, polysilsesquioxane (POSS) one or more.
5. a kind of phosphorus system according to claim 4 synergistic Flame-retardant PET/ABS alloy material, it is characterized in that, described expanding material comprise in methacrylic ester-styrene-butadiene rubber(SBR)-styrol copolymer, methacrylate acrylate-styrol copolymer, acrylate-glycidyl ester-ethene, maleic anhydride stem grafting polyolefin elastomerics, ethylene-acrylate copolymer, ethylene vinyl acetate and acrylonitrile ethylene styrene copolymer one or more.
6. a kind of phosphorus system according to claim 5 synergistic Flame-retardant PET/ABS alloy material, it is characterized in that, described toughner comprises alkylmethacrylate polymer, one or more in acrylonitrile-butadiene-phenylethene grafted copolymer, chlorinatedpolyethylene and ethylacrylate copolymer that acryl-butadiene-styrol copolymer, rubber content are 55 ~ 65%.
7. the preparation method of a kind of phosphorus system according to claim 6 synergistic Flame-retardant PET/ABS alloy material adopts the method extruded of melt blending, it is characterized in that, concrete technological process and blending condition as follows:
(1) dried fire retardant, synergist, expanding material, toughner, oxidation inhibitor are mixed built agent as fire retardant by proportioning in high-speed mixer;
(2) by the built agent of PC/ABS alloy and fire retardant, join melt blending in twin screw extruder and extrude, the temperature that twin screw extruder is each section is 190-235 DEG C, melt extrudes rear tie rod cooling and dicing.
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| CN201310310102.9A CN104327462A (en) | 2013-07-22 | 2013-07-22 | Phosphorus-based synergistically flame-retardant PET/PBS alloy material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832813A (en) * | 2017-01-20 | 2017-06-13 | 广东优科艾迪高分子材料有限公司 | Flame-retardant polyethylene terephthalate resin composition |
| CN106867033A (en) * | 2017-04-10 | 2017-06-20 | 广东优科艾迪高分子材料有限公司 | A kind of inorganic matter cladding organic silicon fibre retardant of alternative antimony oxide and preparation method and application |
| CN112538245A (en) * | 2020-12-04 | 2021-03-23 | 广东晨宝复合材料股份有限公司 | Daylighting tile resin and preparation method thereof |
| CN113248878A (en) * | 2021-04-19 | 2021-08-13 | 厦门毅兴行塑胶原料有限公司 | Halogen-free flame-retardant PET/ABS plastic alloy and preparation method thereof |
| CN115895206A (en) * | 2022-11-21 | 2023-04-04 | 盘锦海兴科技股份有限公司 | Flame-retardant PET material and preparation method thereof |
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2013
- 2013-07-22 CN CN201310310102.9A patent/CN104327462A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832813A (en) * | 2017-01-20 | 2017-06-13 | 广东优科艾迪高分子材料有限公司 | Flame-retardant polyethylene terephthalate resin composition |
| CN106832813B (en) * | 2017-01-20 | 2019-04-23 | 广东优科艾迪高分子材料有限公司 | Flame-retardant polyethylene terephthalate resin composition |
| CN106867033A (en) * | 2017-04-10 | 2017-06-20 | 广东优科艾迪高分子材料有限公司 | A kind of inorganic matter cladding organic silicon fibre retardant of alternative antimony oxide and preparation method and application |
| CN106867033B (en) * | 2017-04-10 | 2019-01-25 | 广东优科艾迪高分子材料有限公司 | A kind of inorganic matter cladding organic silicon fibre retardant of alternative antimony oxide and the preparation method and application thereof |
| CN112538245A (en) * | 2020-12-04 | 2021-03-23 | 广东晨宝复合材料股份有限公司 | Daylighting tile resin and preparation method thereof |
| CN113248878A (en) * | 2021-04-19 | 2021-08-13 | 厦门毅兴行塑胶原料有限公司 | Halogen-free flame-retardant PET/ABS plastic alloy and preparation method thereof |
| CN113248878B (en) * | 2021-04-19 | 2022-12-20 | 厦门毅兴行塑胶原料有限公司 | Halogen-free flame-retardant PET/ABS plastic alloy and preparation method thereof |
| CN115895206A (en) * | 2022-11-21 | 2023-04-04 | 盘锦海兴科技股份有限公司 | Flame-retardant PET material and preparation method thereof |
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Application publication date: 20150204 |