WO2022001016A1 - 一种阻燃abs组合物及其制备方法 - Google Patents
一种阻燃abs组合物及其制备方法 Download PDFInfo
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- WO2022001016A1 WO2022001016A1 PCT/CN2020/136311 CN2020136311W WO2022001016A1 WO 2022001016 A1 WO2022001016 A1 WO 2022001016A1 CN 2020136311 W CN2020136311 W CN 2020136311W WO 2022001016 A1 WO2022001016 A1 WO 2022001016A1
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- flame
- retardant
- phosphorus
- abs composition
- flame retardant
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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 89
- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- -1 triazine compound Chemical class 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910020175 SiOH Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000009916 joint effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009841 combustion method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 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
- 238000005259 measurement Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- C08K2003/2282—Antimonates
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the invention belongs to the technical field of ABS composite materials, and in particular relates to a flame-retardant ABS composition and a preparation method thereof.
- ABS materials are often used as casings for electrical and electronic products. These products will cause fires due to overheating, leakage, and aging of these materials, posing a huge threat to people's lives and property safety.
- the industry's safety standards and standards consistently implement the UL94 standard to evaluate the flame retardant safety of polymer materials due to passive ignition, such as V-2, V-1 and V-0 flame retardant grades.
- the European Union International Electrotechnical Association IE C60695 glow wire standard is used to evaluate its flame retardancy and safety.
- ABS terpolymer contains polybutadiene rubber components, which is flammable. Compared with engineering materials, it is difficult to form carbon during the combustion process. Therefore, it is technically difficult to achieve high-grade flame retardant performance. At present, only halogen V-0 or 5VA flame retardant grades can be achieved, and there is no halogen-free V-0 flame retardant ABS material with excellent mechanical properties.
- the mainstream flame retardant system of halogenated flame retardant ABS at the technical level is the bromine-antimony system, and its popularization and application are also very mature, and it is easy to meet the requirements of UL94-related flame retardant performance testing.
- the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a flame retardant ABS composition.
- the application adopts a variety of flame retardant systems for compounding and synergistic effect. Under the joint action of a variety of flame retardant elements, a higher glow wire performance is achieved, the technical defects of the current flame retardant ABS are solved, and the flame retardant performance of products in the electrical industry is satisfied. skills requirement.
- a flame retardant ABS composition comprising the following components in parts by weight: 36.2-82.7 parts of ABS resin, 12-20 parts of bromine-based flame retardant, antimony-based flame retardant 3 to 10 parts and processing aids 0.2 to 0.8 parts;
- the content of nitrogen is not more than 85000ppm and not less than 7000ppm
- the total content of phosphorus is not more than 50000ppm and not less than 3000ppm
- the total content of fluorine is not more than 40000ppm and not less than 800ppm.
- the flame retardant ABS composition further comprises a nitrogen-based flame retardant, a phosphorus-based flame retardant and a fluorine-containing polymer, the nitrogen element is derived from the nitrogen-based flame retardant and the phosphorus-based flame retardant, and the phosphorus The element is derived from the phosphorus-based flame retardant, and the fluorine element is derived from the fluoropolymer.
- Test method for nitrogen element use oxygen bomb combustion method for pretreatment, and then use ion chromatography for analysis; oxygen bomb combustion method is to take about 5-10g of sample, completely burn it in a closed system of high pressure oxygen, and absorb the sample through alkali solution The residual gas after combustion was measured with an ion chromatograph to measure the peak time and area of elements in the absorption liquid, and quantified with an external standard method.
- Test method for fluorine element use oxygen bomb combustion method for pretreatment, and then use ion chromatography for analysis; oxygen bomb combustion method is to take about 5g-10g sample, completely burn it in a closed system of high pressure oxygen, and absorb the sample through alkali solution For the residual gas of combustion, measure the peak time and area of elements in the absorption liquid with an ion chromatograph, and use the external standard method to quantify.
- Test Method phosphorus element content is: Take 0.4g-0.6g test sample of particles is placed round bottom flask, add 10ml of concentrated H 2 SO 4 and 5ml H 2 O 2, placed on a hot plate of 480 deg.] C until complete digestion is Carbonization takes 35min-45min; after carbonization is completed, cool down for 5min, and then add an appropriate amount of H 2 O 2 to determine whether it is completely carbonized. If not, continue to add H 2 O 2 until complete carbonization, and then cool it in a 100ml volumetric flask. , filtered, centrifuged to take the supernatant, and then the inductively coupled plasma emission spectrometry test ICP.
- the content of fluorine is not more than 40,000 ppm and not less than 1,000 ppm.
- the weight ratio of nitrogen element to phosphorus element is 2.1:1-1.2:1, which has a good flame retardant effect.
- the nitrogen-based flame retardant is a triazine compound, and the structural formula of the triazine compound is as follows:
- R 1 , R 2 and R 3 are the same, and R 1 , R 2 and R 3 are selected from -P(C 6 H 5 ) 2 , -PH 2 O 4 , -P(CH 3 ) 2 , -PH 2 O 2 , -SiH 3 , -SiCl 3 , -SiHCl 2 , -SiHO 3 , -((CH 3 ) 5 Si)2O, -SiOH 2 , -NHR, -NH 2 , -NR 2 , -NCH, -NO 3, -NCO, -N (CH 3 ) or -N 2 Cl.
- the structural formula of the phosphorus-based flame retardant is as follows:
- the degree of polymerization n satisfies: 2 ⁇ n; in the phosphorus-based flame retardant, the mass percentage content of phosphorus is 30%-32%, and the mass percentage content of nitrogen is 14%-16%.
- the above-mentioned phosphorus-based flame retardant has a better condensed phase flame retardant effect, which is beneficial to better suppressing flaming combustion.
- the structural formula of the fluoropolymer is as follows:
- the degree of polymerization n satisfies: 10000 ⁇ n ⁇ 30000.
- the brominated flame retardant is selected from decabromodiphenylethane, brominated epoxy resin, brominated polystyrene, tetrabromobisphenol A, and tris(tribromophenyl)cyanurate. one or more.
- the antimony-based flame retardant is selected from one or more of antimony trioxide, antimony pentoxide and antimonate.
- the processing aid is selected from one or more of hindered phenolic antioxidants, phosphate ester antioxidants, amide lubricants, sulfur-containing compounds, and phosphorus-containing compounds.
- the hindered phenolic antioxidant is selected from one or more of alkyl monophenols, alkyl polyphenols, and thiobisphenols; the lubricant is selected from stearamide lubricants One or more of EBS B50, EB-FF, EBS P400 and WK1890.
- the present invention also provides a method for preparing the flame retardant ABS composition, characterized in that the method is:
- the components are stirred and mixed at a high speed to obtain a premix; the premix is fed into a twin-screw extruder, extruded, cooled with water, and pelletized to obtain a flame-retardant ABS composition.
- the present invention selects the flame retardant ABS composition formula, through the compounding of bromine-based flame retardant, antimony-based flame retardant, nitrogen-based flame retardant, phosphorus-based flame retardant and fluorine-containing polymer, and by controlling nitrogen element,
- the content of phosphorus element and fluorine element, the obtained flame retardant ABS composition has high glow wire performance, which can reach the glow wire grade that is difficult to achieve in the current industry, and can well solve the current defect of poor glow wire performance, especially Suitable for high-grade electrical products.
- the components are uniformly mixed in a high-speed stirring mixer to obtain a premix; the premix is fed into a twin-screw extruder, extruded, cooled with water, and pelletized to obtain a flame-retardant ABS composition;
- the temperature of each section of the screw extruder from the feeding port to the die head is 80°C for the first zone, 160°C for the second zone, 180°C for the third zone, 190°C for the fourth zone, 190°C for the fifth zone, and 190°C for the sixth zone.
- the temperature of the zone is 190°C
- the temperature of the seventh zone is 180°C
- the temperature of the eight zone is 180°C
- the temperature of the nine zone is 180°C
- the temperature of the head is 200°C
- the screw speed is 350rpm
- the length-diameter ratio of the twin-screw extruder is 40.
- test standard of each performance in the embodiment is as shown in Table 1:
- Test items unit Executive standard Tensile Strength MPa ISO527 Bending strength MPa ISO178 Glow Wire Ignition Temperature (GWIT) °C IEC60695.2-12
- Embodiments of the present invention and comparative examples adopt the following raw materials, but are not limited to these raw materials:
- ABS ABS 0215A, Jilin Petrochemical
- Brominated flame retardant Tris (tribromophenyl) cyanurate, FR-245, Israel Chemical;
- Antimony flame retardant antimony trioxide, S-05N, Chenzhou, Changde;
- Triazine compounds the structural formula is Wherein, R1, R2 and R3 are all -NH 2 ;
- Phosphorus flame retardant the structural formula is Among them, n is 3, the P content is 30%, and the N content is 15%;
- Fluoropolymer The structural formula is Among them, 15000 ⁇ n ⁇ 20000
- Antioxidant hindered phenolic antioxidant, IRGANOX 1076;
- Lubricant amide lubricant, EBS, Haosu Chemical
- the present invention sets Examples 1 to 9 and Comparative Examples 1 to 4.
- the components and performance data in specific Examples 1 to 9 and Comparative Examples 1 to 4 are specifically shown in Table 2.
- the brominated flame retardant used is FR-245, the antimony flame retardant is S-05N, the nitrogen flame retardant is triazine compound MCA, the phosphorus flame retardant is JLS-PNPID, and the fluorine-containing polymer is AD541; the nitrogen element comes from nitrogen-based flame retardants and phosphorus-based flame retardants, the phosphorus element comes from phosphorus-based flame retardants, and the fluorine element comes from fluorine-containing polymers; those skilled in the art can pass nitrogen
- the content of the flame retardant and the phosphorus-based flame retardant can be adjusted to obtain the nitrogen element in the specific content of the example; the phosphorus element of the specific content of the embodiment can be obtained by the adjustment of the phosphorus-based flame retardant content; , to obtain the fluorine element of the specific content
- Example 1 to 9 of the present application all have better tensile strength, bending strength and glow wire ignition temperature; It can be seen that the content of fluorine element in Example 7 is greater than 1000, the content of fluorine element in Example 5 is less than 1000, and the tensile strength, bending strength and glow wire ignition temperature in Example 7 are all better than those in Example 5; Comparing Examples 8 and 9 with Example 4, it can be seen that the weight ratio of nitrogen to phosphorus in Example 4 is in the range of 2.1:1 to 1.2:1, and the weight ratio of nitrogen to phosphorus in Examples 8 and 9 is not 2.1. : 1 to 1.2: 1, the tensile strength, flexural strength and glow wire ignition temperature of Example 4 are all better than those of Examples 8 and 9.
- Comparative Example 1 does not contain nitrogen, phosphorus and fluorine, and the tensile strength, flexural strength and glow wire ignition temperature in Comparative Example 1 are significantly worse than those in Example 1; Comparative Example 2 and 3 only contain two kinds of nitrogen, phosphorus and fluorine.
- the tensile strength, flexural strength and glow wire ignition temperature of Comparative Examples 2 to 3 are also worse than those of Example 1; Phosphorus and fluorine, but their contents are not within the scope of the present application, and their tensile strength, flexural strength, and glow-wire ignition temperature are also inferior to those of Example 1.
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种阻燃ABS组合物及其制备方法,包含以下重量份的成分:ABS树脂36.2-82.7份、溴系阻燃剂12-20份、锑系阻燃剂3-10份和加工助剂0.2-0.8份;所述阻燃ABS组合物的总重量中,氮元素的含量不大于85000ppm且不小于7000ppm,磷元素的总含量不大于50000ppm且不小于3000ppm,氟元素总含量不大于40000ppm且不小于800ppm。采用多种阻燃体系进行复配协效,在多种阻燃元素的共同作用下,达到较高的灼热丝性能。
Description
本发明属于ABS复合材料技术领域,具体涉及一种阻燃ABS组合物及其制备方法。
ABS材料常用作电子电器产品的外壳进行应用,这些产品会因过热、漏电、和老化等引燃这些材料而造成火灾,对人们生命和财产安全造成巨大威胁。行业的安全规范标准一致执行UL94标准来评价高分子材料因被动着火的阻燃安全性,如V-2、V-1和V-0阻燃等级。在使用过程中因接触不良、过载、短路而过热的情况采用欧盟国际电工协会IE C60695灼热丝标准来评估其阻燃性及安全性。
ABS三元共聚物化学结构中含有聚丁二烯橡胶组份,具有易燃性,相比工程材料,其在燃烧过程中又难以成炭,因此实现高等级阻燃性能具有较大技术难度,目前只能实现有卤V-0或者5VA阻燃等级,没有力学性能优异的无卤V-0阻燃ABS材料。有卤阻燃ABS在技术层面主流的阻燃体系为溴锑体系,推广应用也非常成熟,容易满足UL94相关的阻燃性能测试要求。但是由于溴锑阻燃体系气相凝聚相阻燃机理的局限性,灼热丝性能较低,难以满足IEC60695标准防火安全性的需要,影响了其在电工产品行业的推广应用。
发明内容
基于此,本发明的目的在于克服上述现有技术的不足之处而提供一种阻燃ABS组合物。本申请采用多种阻燃体系进行复配协效,在多种阻燃元素的共同作用下,达到较高的灼热丝性能,解决目前阻燃ABS的技术缺陷,满足电工行业产品的阻燃性能技术要求。
为实现上述目的,本发明采用的技术方案为:一种阻燃ABS组合物,包含如下重量份的成分:ABS树脂36.2~82.7份、溴系阻燃剂12~20份、锑系阻燃剂3~10份和加工助剂0.2~0.8份;
所述阻燃ABS组合物的总重量中,氮元素的含量不大于85000ppm且不小于7000ppm,磷元素的总含量不大于50000ppm且不小于3000ppm,氟元素总含量不大于40000ppm且不小于800ppm。
优选地,所述阻燃ABS组合物还包括氮系阻燃剂、磷系阻燃剂和含氟聚合物,所述氮元素来自于氮系阻燃剂和磷系阻燃剂,所述磷元素来自于磷系阻燃剂,所述氟元素来自于含氟聚合物。
氮元素的测试方法:采用氧弹燃烧法进行前处理,然后用离子色谱进行分析;氧弹燃烧法是取5-10g左右样品,在高压氧的密闭系统内完全燃烧,通过碱溶液来吸收样品燃烧后的残余气体,用离子色谱仪测量吸收液中元素出峰时间和面积,用外标法定量。
氟元素的测试方法:采用氧弹燃烧法进行前处理,然后用离子色谱进行分析;氧弹燃烧法是取5g-10g左右样品,在高压氧的密闭系统内完全燃烧,通过碱溶液来吸收样品燃烧的残余气体,用离子色谱仪测量吸收液中元素出峰时间和面积,用外标法进行定量。
磷元素的含量的测试方法为:取0.4g-0.6g待测样品粒子置于圆底烧瓶,加10ml浓H
2SO
4和5ml H
2O
2,置于480℃的电热板进行消解直至完全碳化,需要35min-45min;碳化结束后进行冷却5min,然后加适量H
2O
2,判断是否完全碳化,未完全则继续加H
2O
2直至完全碳化,然后在100ml容量瓶中进行冷却定容,过滤,离心取上清液,然后进行电感耦合等离子体发射光谱测试ICP。
优选地,所述阻燃ABS组合物的总重量中,氟元素的含量不大于40000ppm且不小于1000ppm。
优选地,所述阻燃ABS组合物中,氮元素与磷元素的重量比为2.1:1~1.2:1,具有较好的阻燃效果。
优选地,所述氮系阻燃剂为三嗪类化合物,所述三嗪类化合物的结构式如 下:
其中,R
1、R
2、R
3相同,且R
1、R
2、R
3选自-P(C
6H
5)
2、-PH
2O
4、-P(CH
3)
2、-PH
2O
2、-SiH
3、-SiCl
3、-SiHCl
2、-SiHO
3、-((CH
3)
5Si)2O、-SiOH
2、-NHR、-NH
2、-NR
2、-NCH、-NO
3、-NCO、-N(CH
3)或-N
2Cl。
优选地,所述磷系阻燃剂的结构式如下:
其中,聚合度n满足:2≤n;所述磷系阻燃剂中,磷的质量百分含量为30%~32%,氮的质量百分含量为14%~16%。
上述磷系阻燃剂具有较好的凝聚相阻燃效果,有利于更好的抑制有焰燃烧。
优选地,所述含氟聚合物的结构式如下:
其中,聚合度n满足:10000<n<30000。
采用上述含氟聚合物,具有提高抗滴落性能和阻燃性能。
优选地,所述溴系阻燃剂选自十溴二苯乙烷、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A、三(三溴苯基)氰尿酸酯中的一种或几种。
优选地,所述锑系阻燃剂选自三氧化二锑、五氧化二锑、锑酸盐中的一种或几种。
优选地,所述加工助剂选自受阻酚类抗氧剂、磷酸酯类抗氧剂、酰胺类润 滑剂、含硫化合物、含磷化合物中的一种或几种。
更优选地,所述受阻酚类抗氧剂选自烷基单酚类,烷基多酚类、硫代双酚类中的一种或几种;所述润滑剂选自硬脂酰胺类润滑剂EBS B50、EB-FF、EBS P400、WK1890中的一种或几种。
同时,本发明还提供一种所述的阻燃ABS组合物的制备方法,其特征在于,所述方法为:
将各成分高速搅拌混合均匀,得到预混料;将预混料送入双螺杆挤出机中,挤出、过水冷却、造粒,得到阻燃ABS组合物。
相对于现有技术,本发明的有益效果为:
本发明选用阻燃ABS组合物配方中,通过溴系阻燃剂、锑系阻燃剂、氮系阻燃剂、磷系阻燃剂、含氟聚合物的复配,并通过控制氮元素、磷元素、氟元素的含量,得到的阻燃ABS组合物具有较高的灼热丝性能,可以达到目前行业内难以实现的灼热丝等级,且能很好的解决目前灼热丝性能差的缺陷,特别适用于高等级的电工类产品。
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明实施例中ABS复合材料的制备方法为:
将各成分在高速搅拌混料机混合均匀,得到预混料;将预混料送入双螺杆挤出机中,挤出、过水冷却、造粒,得到阻燃ABS组合物;其中,双螺杆挤出机的各段螺杆温度从加料口到机头的温度分别为一区温度80℃、二区温度160℃、三区温度180℃、四区温度190℃、五区温度190℃、六区温度190℃、七区温度180℃、八区温度180℃、九区温度180℃、机头温度200℃,螺杆转速为350rpm,双螺杆挤出机的长径比为40。
实施例中各性能的测试标准如表1所示:
表1各性能的测量标准
检测项目 | 单位 | 执行标准 |
拉伸强度 | MPa | ISO527 |
弯曲强度 | MPa | ISO178 |
灼热丝起燃温度(GWIT) | ℃ | IEC60695.2-12 |
本发明的实施例及对比例采用如下原料,但不仅限于这些原料:
ABS:ABS 0215A,吉林石化;
溴系阻燃剂:三(三溴苯基)氰尿酸酯,FR-245,以色列化工;
锑系阻燃剂:三氧化二锑,S-05N,常德辰州;
加工助剂:抗氧剂和润滑剂的重量比为1:3;
抗氧剂:受阻酚类抗氧剂,IRGANOX 1076;
润滑剂:酰胺类润滑剂,EBS,昊塑化工;
本发明设置实施例1~9和对比例1~4,具体实施例1~9和对比例1~4中的各成分及性能数据,具体如表2所示,本申请实施例及对比例中用到的溴系阻燃剂为FR-245,锑系阻燃剂为S-05N,氮系阻燃剂为三嗪类化合物MCA,磷系阻燃剂为JLS-PNPID,含氟聚合物为AD541;所述氮元素来自于氮系阻燃剂和磷系阻燃剂,所述磷元素来自于磷系阻燃剂,所述氟元素来自于含氟聚合物;本 领域技术人员可通过氮系阻燃剂和磷系阻燃剂含量的调配,得到实施例特定含量的氮元素;通过磷系阻燃剂含量的调配,得到实施例特定含量的磷元素;通过含氟聚合物含量的调配,得到实施例特定含量的氟元素。
表2实施例1~9和对比例1~4中的各成分及性能数据
从表2可以看出,与对比例1~4相比,本申请实施例1~9均具有较好的拉伸强度、弯曲强度及灼热丝起燃温度;将实施例5和实施例7对比可知,实施例7中氟元素的含量大于1000,实施例5中的氟元素含量小于1000,实施例7中的拉伸强度、弯曲强度及灼热丝起燃温度均好于实施例5;将实施例8、9与实施例4对比可知,实施例4中氮元素与磷元素的重量比在2.1:1~1.2:1范围内,实施例8、9中氮元素与磷元素的重量比不在2.1:1~1.2:1范围,实施例4的拉伸强度、弯曲强度及灼热丝起燃温度均好于实施例8、9。
将实施例1与对比例1对比可知,对比例1中不含有氮、磷、氟,对比例1中的拉伸强度、弯曲强度、灼热丝起燃温度均明显差于实施例1;对比例2、3中只含有氮、磷、氟中的两种,对比例2~3中的拉伸强度、弯曲强度、灼热丝 起燃温度也差于实施例1;对比例4中虽然含有氮、磷、氟,但是其含量都不在本申请范围内,其拉伸强度、弯曲强度、灼热丝起燃温度也差于实施例1。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
- 一种阻燃ABS组合物,其特征在于,包含如下重量份的成分:ABS树脂36.2~82.7份、溴系阻燃剂12~20份、锑系阻燃剂3~10份和加工助剂0.2~0.8份;所述阻燃ABS组合物的总重量中,氮元素的含量不大于85000ppm且不小于7000ppm,磷元素的总含量不大于50000ppm且不小于3000ppm,氟元素总含量不大于40000ppm且不小于800ppm。
- 如权利要求1所述的阻燃ABS组合物,其特征在于,所述阻燃ABS组合物还包括氮系阻燃剂、磷系阻燃剂和含氟聚合物,所述氮元素来自于氮系阻燃剂和磷系阻燃剂,所述磷元素来自于磷系阻燃剂,所述氟元素来自于含氟聚合物。
- 如权利要求1所述的阻燃ABS组合物,其特征在于,所述阻燃ABS组合物的总重量中,氟元素的含量不大于40000ppm且不小于1000ppm。
- 如权利要求1所述的阻燃ABS组合物,其特征在于,所述阻燃ABS组合物中,氮元素与磷元素的重量比为2.1:1~1.2:1。
- 如权利要求1所述的阻燃ABS组合物,其特征在于,所述溴系阻燃剂选自十溴二苯乙烷、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A、三(三溴苯基)氰尿酸酯中的一种或几种;所述锑系阻燃剂选自三氧化二锑、五氧化二锑、锑酸盐中的一种或几种。
- 如权利要求1所述的阻燃ABS组合物,其特征在于,所述加工助剂选自受阻酚类抗氧剂、磷酸酯类抗氧剂、酰胺类润滑剂、含硫化合物、含磷化合物中的一种或几种。
- 一种如权利要求1~9任一项所述的阻燃ABS组合物的制备方法,其特征在于,所述方法为:将各成分高速搅拌混合均匀,得到预混料;将预混料送入双螺杆挤出机中,挤出、过水冷却、造粒,得到阻燃ABS组合物。
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