WO2023160148A1 - Flame-retardant polycarbonate composition, preparation method therefor and application thereof - Google Patents

Flame-retardant polycarbonate composition, preparation method therefor and application thereof Download PDF

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WO2023160148A1
WO2023160148A1 PCT/CN2022/139284 CN2022139284W WO2023160148A1 WO 2023160148 A1 WO2023160148 A1 WO 2023160148A1 CN 2022139284 W CN2022139284 W CN 2022139284W WO 2023160148 A1 WO2023160148 A1 WO 2023160148A1
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flame
polycarbonate composition
flame retardant
retardant
phosphorus
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PCT/CN2022/139284
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French (fr)
Chinese (zh)
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彭民乐
陈平绪
叶南飚
杨燕
吴俊�
艾军伟
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金发科技股份有限公司
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    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • C08K2003/328—Phosphates of heavy metals
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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 relates to the technical field of flame retardant materials, in particular to a flame retardant polycarbonate composition and its preparation method and application.
  • PC Polycarbonate
  • the content of silicone flame retardant in PC is generally below 4%.
  • the modified material will hardly lose the physical and mechanical properties of the original PC resin, but the flame retardant efficiency is limited.
  • the combination of conventional flame retardants and layered inorganic compounds can improve the flame retardant performance, but it will reduce the processing performance of the material.
  • the object of the present invention is to overcome the disadvantages of the above-mentioned prior art and provide a polycarbonate composition with good flame retardancy and toughness, its preparation method and application.
  • a flame-retardant polycarbonate composition comprising the following components by weight: 100 parts of polycarbonate, 3-10 parts of phosphorus-containing flame retardant and 1-5 parts of zirconium phosphate;
  • the phosphorus-containing flame retardant is at least one of phosphazene flame retardants, phosphate ester flame retardants, and phosphaphenanthrene flame retardants.
  • the invention greatly improves the flame retardant efficiency by compounding the phosphorus-containing flame retardant and the layered inorganic compound phase of zirconium phosphate, and the zirconium phosphate plays a synergistic flame retardant effect, which can strengthen the compactness of the carbon layer after combustion, and stabilize coagulation phase structure. In addition, it has good flow performance, and is especially suitable for forming thin-walled large parts.
  • the phosphazene flame retardant is at least one of hexaphenoxycyclotriphosphazene, hexachlorocyclotriphosphazene, aminocyclotriphosphazene, hydroxyl cyclotriphosphazene, and double bond-containing cyclotriphosphazene
  • the phosphate ester flame retardant is 1,3-phenylene phosphate tetrakis (2,6-xylyl) ester, tris (2-chloropropyl) phosphate, condensed phosphoric acid ester, resorcinol At least one of bis(diphenyl phosphate); the phosphaphenanthrene flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • the phosphorus-containing flame retardant is a compound of hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene in a weight ratio of 1:(1-4).
  • Hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene can act synergistically; at the initial stage of combustion, hexachlorocyclotriphosphazene has high activity, and the phosphoric acid, metaphosphoric acid and polyphosphoric acid generated by thermal decomposition can quickly dissolve in the polymer
  • a dense non-volatile protective film is formed on the surface of the material to isolate the air; in addition, after being heated, gases such as carbon dioxide, ammonia, nitrogen, and water vapor are released to dilute combustible gases and reduce combustion.
  • the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (3-10):1.
  • the organic phosphorus in the phosphorus-containing flame retardant decomposes to generate oxyphosphoric acid.
  • This acid can catalyze the dehydration of the polycarbonate hydroxyl to form a carbon covering on the surface to form an isolation layer. Due to the poor thermal conductivity of the isolation layer, the surface temperature of the polycarbonate is low. On the one hand It can reduce the heat release amount and release rate, and reduce the mass loss.
  • the gas product PO formed by the pyrolysis of phosphorus flame retardants can capture free radicals H and OH, and play a role in inhibiting the combustion chain reaction.
  • the addition of phosphorus-containing flame retardants is high, which will lead to a decrease in impact.
  • zirconium phosphate as an inorganic substance will reduce the impact performance and flow performance of the composite material.
  • the inventors of the present application have found through a large number of experiments that the combination of the two can maintain high impact and high flow while achieving high flame retardancy.
  • Zirconium phosphate can catalyze phosphorus-containing flame retardants to form a bridge structure, reduce the volatilization of P-O compounds during pyrolysis, and save more P to promote carbon formation; the two synergistically achieve the same flame-retardant effect while reducing phosphorus-containing
  • the amount of flame retardant is used to maintain a high impact strength.
  • zirconium phosphate is an inorganic substance.
  • the impact strength will be reduced, and due to adsorption, it will absorb phosphorus-containing flame retardants, reducing the flame retardant efficiency.
  • the content of zirconium phosphate is too high, it will reduce the flame retardancy;
  • the zirconium phosphate content is too low, the barrier effect of the layered structure of zirconium phosphate is not enough to promote the carbonation of phosphorus-containing flame retardants.
  • both flame retardancy and impact resistance can be taken into account.
  • the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (5-8):1.
  • the inventors of the present application have confirmed through experiments that when the weight ratio of the two complies with this limit, the flame retardancy, impact resistance and fluidity are optimal.
  • the flame retardant polycarbonate composition also includes 0.1 to 1 parts of auxiliary agents; the auxiliary agents are stabilizers, antioxidants, flame retardants, lubricants, anti-dripping agents, mold release agents, At least one of plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
  • auxiliary agents are stabilizers, antioxidants, flame retardants, lubricants, anti-dripping agents, mold release agents, At least one of plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
  • the auxiliary agent is a mixture of 0.1-0.2 parts of antioxidant and 0.2-0.8 parts of filler.
  • Described antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 2246, antioxidant 245, antioxidant 168, antioxidant B-CAP, antioxidant PEP-36, antioxidant S- At least one of 680 etc.
  • the filler is at least one of talcum powder, wollastonite, mica and the like. Adding an antioxidant can improve the anti-aging performance of the polycarbonate composition, and adding a filler can improve processing performance and further improve the flame retardancy of the material.
  • the filler is a compound of two talcum powders, one kind of talcum powder has a D50 particle size of 1 to 3 ⁇ m, and one kind of talcum powder has a D50 particle size of 8 to 12 ⁇ m, and the weight ratio of the two is 1: (1 ⁇ 3).
  • the layered structure of talc powder and the combined water in the molecule can reduce the heat of combustion and combustible substances.
  • the talc powder with large particle size (8-12 ⁇ m) plays a supporting role in the carbon layer, and the talc powder with small particle size can enhance the carbon layer. Continuity and increased density, the two synergistically improve the stability of the carbon layer.
  • the invention also discloses a preparation method of the flame retardant polycarbonate composition, the preparation method is: adding each component into a high mixer according to the proportion and mixing them evenly; Melt extrusion and granulation to obtain the flame-retardant polycarbonate composition; the aspect ratio of the twin-screw extruder (36-56): 1, the screw temperature of 270-290°C, and the rotation speed of 200-600r/min.
  • the invention also discloses the application of the flame-retardant polycarbonate composition in the fields of automobiles, electronics, home appliances and construction.
  • the beneficial effects of the present invention are as follows: the present invention significantly improves the flame retardancy of the polycarbonate composition by compounding phosphorus-containing flame retardants with zirconium phosphate;
  • the type of flame retardant and the type of filler are selected to ensure that the polycarbonate composition has good toughness while improving the flame retardancy of the polycarbonate composition. It is suitable for use in the fields of automobiles, electronics, home appliances, construction, etc. application.
  • Polycarbonate FN 1900, Idemitsu;
  • Phosphorus-containing flame retardant 1 hexachlorocyclotriphosphazene, industrial grade (99%), Aladdin's reagent;
  • Phosphorus-containing flame retardant 2 condensed phosphoric acid ester, FP-600, Adico;
  • Phosphorus-containing flame retardant 3 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, HCA, Japan Sanko Company;
  • Phosphorus-containing flame retardant 4 Hexaphenoxycyclotriphosphazene, Weihai Kingway;
  • Phosphorus-containing flame retardant 5 1,3-phenylene phosphate tetrakis (2,6-xylyl) ester, PX-200, Japan Daihachi Chemical Industry Co., Ltd.;
  • Phosphorus-containing flame retardant 6 organic phosphinic acid, FP-110, Japan FUSHIMI;
  • Phosphorus-containing flame retardant 7 resorcinol bis(diphenyl phosphate), Sol-DP, ICP-IP;
  • Talc powder 1 HTPUltra5L, D50 particle size is 2 ⁇ m, Aihai barley talc powder;
  • Talc powder 2 SDC-9489, D50 particle size is 5 ⁇ m, Xinda talc powder;
  • Talc powder 3 AH-1250Y, D50 particle size is 10 ⁇ m, Aihai talc powder;
  • Antioxidant 1010 Antioxidant 1010, commercially available.
  • the antioxidants used in the following examples and comparative examples are all the same.
  • Examples of the flame retardant polycarbonate composition of the present invention the formulations of Examples 1 to 23 are shown in Table 1.
  • the preparation method is as follows: add each component into a high mixer according to the proportion and mix them uniformly; then melt and extrude in a twin-screw extruder, and granulate to obtain the flame-retardant polycarbonate composition;
  • the aspect ratio is 40:1, the screw temperature is 280°C, and the rotation speed is 300r/min.
  • Comparative Examples 1-3 are flame-retardant polycarbonate compositions, the formula of which is shown in Table 1, and the preparation method is the same as that of Example 1.
  • test standard is as follows:
  • Liquidity The length of the flow of the Archimedes helix.
  • the spiral interface is rectangular with a width of 5 mm and a thickness of 1.4 mm.
  • the sample is injection-molded with an Archimedes spiral mold at 280°C, where the injection pressure is 50%, and the injection speed is 50%. After the part is taken out, the length is read, and the length of 10 samples is recorded, and the average length is recorded , the unit is mm;
  • Example 1 488 5.2 428
  • Example 2 478 6.3 403
  • Example 3 475 6.8 405
  • Example 4 465 6.8 398
  • Example 5 451 7.3 385
  • Example 6 469 6.7 386
  • Example 7 459 7.1 389
  • Example 8 450 7.3 384
  • Example 9 450 7.1 371
  • Example 10 433 7.7
  • Example 11 432 7.8 375
  • Example 12 430 7.5 373
  • Example 13 438 7.6 379
  • Example 14 448 7.4 382
  • Example 15 440 7.9 370
  • Example 16 470 6.8 403
  • Example 17 522 2.1 456
  • Example 18 509 4.2 433
  • Example 19 511 3.3 445
  • Example 20 492 5.1 430
  • Example 21 490 5.5 431
  • Example 22 479 5.8 432
  • Example 23 475 6.1 428 Comparative example 1 420 26.6 321 Comparative example 2 386 12.3 313 Comparative example 3 346 56.1 147
  • the helix lengths of the polycarbonate compositions described in Examples 1 to 23 are all greater than 430mm, and have good fluidity; t1+t2 are all within 10s, meeting the V-0 requirements of UL94-2015; The impact strength is higher than 370J/m, with good impact resistance.
  • the phosphorus-containing compound used in Comparative Example 1 is an organic phosphinic acid.
  • the flame retardant performance is significantly worse; In Comparative Example 2, only phosphorus-containing flame retardants were added, and the flame retardancy and impact resistance were poor; in Comparative Example 3, only zirconium phosphate compounds were added, and the flame retardant effect was poor, and the fluidity decreased significantly.
  • Examples 17 to 23 Comparing the test results of Examples 1-16 with Examples 17-23, it can be seen that the comprehensive performance of the polycarbonate composition added with talc powder is obviously better.
  • the length of the helix in Examples 17 to 19 is more than 500mm
  • t1+t2 is less than 5s
  • the notched impact strength is more than 430J/m, which has good fluidity, flame retardancy and Impact resistance
  • the results show that the combination of talc powder with a particle size of 1 to 3 ⁇ m and talc powder with a particle size of 8 to 12 ⁇ m at a weight ratio of 1: (1 to 3) can synergistically improve the overall performance of the polycarbonate composition .
  • Example 5 Comparing the test results of Example 4 and Example 5, it can be seen that although the total weight of phosphorus-containing flame retardant and zirconium phosphate in Example 5 is higher than that of Example 4, the proportion of zirconium phosphate is too high.
  • the weight ratio of the phosphorus flame retardant is not in the range of 1:(3-10), which will affect the flame retardancy of the polycarbonate composition instead.

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Abstract

The present invention provides a flame-retardant polycarbonate composition, a preparation method therefor and an application thereof, and relates to the technical field of flame-retardant materials. The flame-retardant polycarbonate composition comprises the following components in part by weight: 100 parts of polycarbonate, 3-10 parts of phosphorus-containing flame retardant, and 1-5 parts of zirconium phosphate. The phosphorus-containing flame retardant is at least one of a phosphazene flame retardant, a phosphate flame retardant, and a phosphaphenanthrene flame retardant. According to the present invention, the phosphorus-containing flame retardant and the zirconium phosphate are compounded, such that the polycarbonate composition with good flame retardance and toughness is prepared, and the polycarbonate composition is suitable for the fields of automobiles, electronics, household appliances, buildings and the like.

Description

一种阻燃聚碳酸酯组合物及其制备方法与应用A kind of flame retardant polycarbonate composition and its preparation method and application 技术领域technical field
本发明涉及阻燃材料技术领域，尤其涉及一种阻燃聚碳酸酯组合物及其制备方法与应用。The invention relates to the technical field of flame retardant materials, in particular to a flame retardant polycarbonate composition and its preparation method and application.
背景技术Background technique
聚碳酸酯(PC)是一种综合性能优良的工程塑料,抗冲击性能居热塑性塑料之首,尺寸稳定性好，热变形温度高(130～140℃)，其他如耐候性及电性能也都十分优异。在汽车、电子、家电、建筑等行业都得到了大量的应用。PC树脂的氧指数达26％，离火能自熄。市面上商品化的PC树脂按照美国UL94标准进行阻燃性能评价，大多数能达到V-2等级。但实际应用中，人们希望它能达到UL94V-0等级，所以需要对PC进行阻燃改性。Polycarbonate (PC) is an engineering plastic with excellent comprehensive properties. Its impact resistance ranks first among thermoplastics. It has good dimensional stability and high heat distortion temperature (130-140 ° C). Very good. It has been widely used in industries such as automobiles, electronics, home appliances, and construction. The oxygen index of PC resin reaches 26%, and it can self-extinguish when it is away from the fire. Commercialized PC resins on the market are evaluated for flame retardancy according to the American UL94 standard, and most of them can reach the V-2 level. However, in practical applications, people hope that it can reach the UL94V-0 level, so PC needs to be modified for flame retardancy.
家电的发展趋势是薄壁化，要求材料具有更高的尺寸精度，适应更自由的设计度，同时要求更高的阻燃水平。在现有的PC阻燃剂中，磷酸三苯酯(TPP)、双酚A-双(二苯基磷酸酯)(BDP)等传统磷酸酯类阻燃剂存在配方添加量大、工艺要求高、对力学性能影响严重等缺点；磺酸盐体系添加量少，对分散工艺要求高，且本身易吸潮，并且水解稳定性较差，可能对环境造成危害，限制了其应用范围。有机硅阻燃PC具有很多优点，在PC中的有机硅阻燃剂含量一般在4％以下,改性后的材料几乎不会损失原PC树脂的物理机械性能，但阻燃效率有限。常规阻燃剂和层状无机化合物复配可以提高阻燃性能，但会降低材料的加工性能。The development trend of home appliances is thin-walled, requiring materials with higher dimensional accuracy, adapting to a more free design, and requiring a higher level of flame retardancy. Among the existing PC flame retardants, traditional phosphate flame retardants such as triphenyl phosphate (TPP) and bisphenol A-bis(diphenyl phosphate) (BDP) have a large amount of formula addition and high process requirements. , Serious impact on mechanical properties and other disadvantages; the addition of sulfonate system is small, the requirements for dispersion process are high, and it is easy to absorb moisture, and its hydrolytic stability is poor, which may cause harm to the environment and limit its application range. Silicone flame retardant PC has many advantages. The content of silicone flame retardant in PC is generally below 4%. The modified material will hardly lose the physical and mechanical properties of the original PC resin, but the flame retardant efficiency is limited. The combination of conventional flame retardants and layered inorganic compounds can improve the flame retardant performance, but it will reduce the processing performance of the material.
发明内容Contents of the invention
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具有良好的阻燃性和韧性的聚碳酸酯组合物及其制备方法与应用。The object of the present invention is to overcome the disadvantages of the above-mentioned prior art and provide a polycarbonate composition with good flame retardancy and toughness, its preparation method and application.
为实现上述目的，本发明所采取的技术方案为：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种阻燃聚碳酸酯组合物，所述阻燃聚碳酸酯组合物包含如下重量份的成分：聚碳酸酯100份、含磷阻燃剂3～10份和磷酸锆1～5份；所述含磷阻燃剂为磷腈阻燃剂、磷酸酯类阻燃剂、磷杂菲类阻燃剂中的至少一种。A flame-retardant polycarbonate composition, the flame-retardant polycarbonate composition comprising the following components by weight: 100 parts of polycarbonate, 3-10 parts of phosphorus-containing flame retardant and 1-5 parts of zirconium phosphate; The phosphorus-containing flame retardant is at least one of phosphazene flame retardants, phosphate ester flame retardants, and phosphaphenanthrene flame retardants.
本发明通过含磷阻燃剂和磷酸锆层状无机化合物相的复配，大幅提高了阻燃效率，磷酸锆起到协效阻燃的作用，可以加强燃烧后碳层的致密性，稳定凝聚相结构。此外，流动性能好，特别适用于薄壁大制件的成型。The invention greatly improves the flame retardant efficiency by compounding the phosphorus-containing flame retardant and the layered inorganic compound phase of zirconium phosphate, and the zirconium phosphate plays a synergistic flame retardant effect, which can strengthen the compactness of the carbon layer after combustion, and stabilize coagulation phase structure. In addition, it has good flow performance, and is especially suitable for forming thin-walled large parts.
优选地，所述磷腈阻燃剂为六苯氧基环三磷腈、六氯环三磷腈、氨基环三磷腈、羟基环三磷腈、含双键环三磷腈中的至少一种；所述磷酸酯类阻燃剂为1,3-亚苯基磷酸四(2,6-二甲苯基)酯、磷酸三(2-氯丙基)酯、缩合磷酸酯、间苯二酚双(二苯基磷酸酯)中的至少一种；所述磷杂菲类阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物。Preferably, the phosphazene flame retardant is at least one of hexaphenoxycyclotriphosphazene, hexachlorocyclotriphosphazene, aminocyclotriphosphazene, hydroxyl cyclotriphosphazene, and double bond-containing cyclotriphosphazene The phosphate ester flame retardant is 1,3-phenylene phosphate tetrakis (2,6-xylyl) ester, tris (2-chloropropyl) phosphate, condensed phosphoric acid ester, resorcinol At least one of bis(diphenyl phosphate); the phosphaphenanthrene flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
优选地，所述含磷阻燃剂为六氯环三磷腈和六苯氧基环三磷腈重量比为1:(1～4)的复配物。六氯环三磷腈和六苯氧基环三磷腈可协同作用；在燃烧初期，六氯环三磷腈活性高，其受热分解生成的磷酸、偏磷酸和聚磷酸，可迅速在聚合物材料的表面形成致密不挥发性保护膜，隔绝了空气；此外，受热后放出二氧化碳、氨气、氮气、水蒸汽等气体稀释可燃气体，减少燃烧。但六氯环三磷腈稳定性不足，在燃烧后期，高热稳定的六苯氧基环三磷腈可与火焰区域中的H·、HO·活性基团结合，起到抑制火焰的作用，终止链反应；两者协同作用，体系表现出良好的阻燃性能。Preferably, the phosphorus-containing flame retardant is a compound of hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene in a weight ratio of 1:(1-4). Hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene can act synergistically; at the initial stage of combustion, hexachlorocyclotriphosphazene has high activity, and the phosphoric acid, metaphosphoric acid and polyphosphoric acid generated by thermal decomposition can quickly dissolve in the polymer A dense non-volatile protective film is formed on the surface of the material to isolate the air; in addition, after being heated, gases such as carbon dioxide, ammonia, nitrogen, and water vapor are released to dilute combustible gases and reduce combustion. However, the stability of hexachlorocyclotriphosphazene is insufficient. In the later stage of combustion, the highly thermally stable hexaphenoxycyclotriphosphazene can combine with the H , HO active groups in the flame area to inhibit the flame and terminate the flame. Chain reaction; the synergistic effect of the two, the system shows good flame retardant performance.
优选地，所述含磷阻燃剂与磷酸锆的重量比为(3～10):1。含磷阻燃剂中的有机磷分解生成磷氧酸，这种酸能催化聚碳酸酯羟基脱水成炭覆盖在表面形成隔离层，由于此隔离层导热性差使聚碳酸酯表面温度低，一方面能降低热释放量和释放速率，降低质量损失，另一方面磷阻燃剂热裂解所形成的气体产物PO·可以捕获游离基H·和·OH，起到抑制燃烧链锁反应的作用。但为了达到阻隔作用，含磷阻燃剂添加量高，会导致冲击性下降。Preferably, the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (3-10):1. The organic phosphorus in the phosphorus-containing flame retardant decomposes to generate oxyphosphoric acid. This acid can catalyze the dehydration of the polycarbonate hydroxyl to form a carbon covering on the surface to form an isolation layer. Due to the poor thermal conductivity of the isolation layer, the surface temperature of the polycarbonate is low. On the one hand It can reduce the heat release amount and release rate, and reduce the mass loss. On the other hand, the gas product PO formed by the pyrolysis of phosphorus flame retardants can capture free radicals H and OH, and play a role in inhibiting the combustion chain reaction. However, in order to achieve the barrier effect, the addition of phosphorus-containing flame retardants is high, which will lead to a decrease in impact.
磷酸锆层状结构稳定，具有隔热隔氧及减缓可燃性气体逸出、延缓降解、同时促进成炭的作用；此外，磷酸锆会释放出结晶水，降低了气相燃烧区中可 燃物的浓度并吸收大量的热量，延缓聚合物基体热分解并降低燃烧速度，从而增强了聚合物的阻燃性。但磷酸锆作为无机物会降低复合材料的冲击性能和流动性能。The layered structure of zirconium phosphate is stable, which has the functions of heat and oxygen insulation, slowing the escape of combustible gases, delaying degradation, and promoting char formation; in addition, zirconium phosphate will release crystal water, which reduces the concentration of combustibles in the gas phase combustion zone And absorb a large amount of heat, delay the thermal decomposition of the polymer matrix and reduce the burning speed, thereby enhancing the flame retardancy of the polymer. However, zirconium phosphate as an inorganic substance will reduce the impact performance and flow performance of the composite material.
本申请发明人通过大量的实验发现，两者复配，在达到高阻燃的同时，保持高冲击和高流动。磷酸锆可以催化含磷阻燃剂形成桥联结构，减少热解过程中P-O化合物的挥发，保存更多的P以促进成碳；两者协效，达到相同阻燃效果的同时，降低含磷阻燃剂的用量，保持较高的冲击强度。The inventors of the present application have found through a large number of experiments that the combination of the two can maintain high impact and high flow while achieving high flame retardancy. Zirconium phosphate can catalyze phosphorus-containing flame retardants to form a bridge structure, reduce the volatilization of P-O compounds during pyrolysis, and save more P to promote carbon formation; the two synergistically achieve the same flame-retardant effect while reducing phosphorus-containing The amount of flame retardant is used to maintain a high impact strength.
但磷酸锆是无机物，当含量过高，作为应力集中点会降低冲击强度，且由于吸附作用，会吸附含磷阻燃剂，降低阻燃效率，磷酸锆含量过高反而降低阻燃性；当磷酸锆含量过低，磷酸锆层状结构的阻隔作用还不足以提升含磷阻燃剂的成碳，当两者的重量比符合上述限定时可以兼顾阻燃性和抗冲击性能。However, zirconium phosphate is an inorganic substance. When the content is too high, as a stress concentration point, the impact strength will be reduced, and due to adsorption, it will absorb phosphorus-containing flame retardants, reducing the flame retardant efficiency. If the content of zirconium phosphate is too high, it will reduce the flame retardancy; When the zirconium phosphate content is too low, the barrier effect of the layered structure of zirconium phosphate is not enough to promote the carbonation of phosphorus-containing flame retardants. When the weight ratio of the two meets the above limits, both flame retardancy and impact resistance can be taken into account.
进一步优选地，所述含磷阻燃剂和磷酸锆的重量比为(5～8):1。本申请发明人通过实验证实，当两者的重量比符合该限定时，阻燃性、抗冲击性和流动性最优。Further preferably, the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (5-8):1. The inventors of the present application have confirmed through experiments that when the weight ratio of the two complies with this limit, the flame retardancy, impact resistance and fluidity are optimal.
优选地，所述阻燃聚碳酸酯组合物还包含助剂0.1～1份；所述助剂为稳定剂、抗氧剂、阻燃剂、润滑剂、抗滴落剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的至少一种。Preferably, the flame retardant polycarbonate composition also includes 0.1 to 1 parts of auxiliary agents; the auxiliary agents are stabilizers, antioxidants, flame retardants, lubricants, anti-dripping agents, mold release agents, At least one of plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
优选地，所述助剂为抗氧剂0.1～0.2份和填料0.2～0.8份的混合物。所述抗氧剂为抗氧剂1076、抗氧剂1010、抗氧剂2246、抗氧剂245、抗氧剂168、抗氧剂B-CAP、抗氧剂PEP-36、抗氧剂S-680等中的至少一种。所述填料为滑石粉、硅灰石、云母等中的至少一种。添加抗氧剂可以改善聚碳酸酯组合物的抗老化性能，添加填料可以改善加工性能，进一步提高材料的阻燃性。Preferably, the auxiliary agent is a mixture of 0.1-0.2 parts of antioxidant and 0.2-0.8 parts of filler. Described antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 2246, antioxidant 245, antioxidant 168, antioxidant B-CAP, antioxidant PEP-36, antioxidant S- At least one of 680 etc. The filler is at least one of talcum powder, wollastonite, mica and the like. Adding an antioxidant can improve the anti-aging performance of the polycarbonate composition, and adding a filler can improve processing performance and further improve the flame retardancy of the material.
优选地，所述填料为两种滑石粉的复配物，一种滑石粉的D50粒径为1～3μm，一种滑石粉的D50粒径为8～12μm，两者的重量比为1:(1～3)。Preferably, the filler is a compound of two talcum powders, one kind of talcum powder has a D50 particle size of 1 to 3 μm, and one kind of talcum powder has a D50 particle size of 8 to 12 μm, and the weight ratio of the two is 1: (1~3).
滑石粉的层状结构及分子内结合水，具有降低燃烧热和可燃物质的作用，大粒径(8～12μm)的滑石粉在碳层中其支撑作用，小粒径的滑石粉提升碳层连 贯性及提升致密程度，两者协效提高碳层稳定。The layered structure of talc powder and the combined water in the molecule can reduce the heat of combustion and combustible substances. The talc powder with large particle size (8-12 μm) plays a supporting role in the carbon layer, and the talc powder with small particle size can enhance the carbon layer. Continuity and increased density, the two synergistically improve the stability of the carbon layer.
同时，本发明还公开了一种所述阻燃聚碳酸酯组合物的制备方法，所述制备方法为：按配比将各组分加入高混机中混合均匀；然后在双螺杆挤出机中熔融挤出，造粒，得到所述阻燃聚碳酸酯组合物；双螺杆挤出机的长径比(36～56):1，螺杆温度270～290℃，转速为200～600r/min。At the same time, the invention also discloses a preparation method of the flame retardant polycarbonate composition, the preparation method is: adding each component into a high mixer according to the proportion and mixing them evenly; Melt extrusion and granulation to obtain the flame-retardant polycarbonate composition; the aspect ratio of the twin-screw extruder (36-56): 1, the screw temperature of 270-290°C, and the rotation speed of 200-600r/min.
此外，本发明还公开了所述阻燃聚碳酸酯组合物在汽车、电子、家电、建筑领域的应用。In addition, the invention also discloses the application of the flame-retardant polycarbonate composition in the fields of automobiles, electronics, home appliances and construction.
相比于现有技术，本发明的有益效果为：本发明通过选用含磷阻燃剂和磷酸锆复配，显著提升了聚碳酸酯组合物的阻燃性，并且，本发明还对含磷阻燃剂的种类和填料的种类进行选择，在提高聚碳酸酯组合物的阻燃性的同时保证了聚碳酸酯组合物具有良好的韧性，适于在汽车、电子、家电、建筑等领域中应用。Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention significantly improves the flame retardancy of the polycarbonate composition by compounding phosphorus-containing flame retardants with zirconium phosphate; The type of flame retardant and the type of filler are selected to ensure that the polycarbonate composition has good toughness while improving the flame retardancy of the polycarbonate composition. It is suitable for use in the fields of automobiles, electronics, home appliances, construction, etc. application.
具体实施方式Detailed ways
为更好地说明本发明的目的、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。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples.
实施例和对比例使用的材料如下：The materials used in Examples and Comparative Examples are as follows:
聚碳酸酯：FN 1900，日本出光；Polycarbonate: FN 1900, Idemitsu;
含磷阻燃剂1：六氯环三磷腈，工业级(99％)，阿拉丁试剂；Phosphorus-containing flame retardant 1: hexachlorocyclotriphosphazene, industrial grade (99%), Aladdin's reagent;
含磷阻燃剂2：缩合磷酸酯，FP-600，艾迪科；Phosphorus-containing flame retardant 2: condensed phosphoric acid ester, FP-600, Adico;
含磷阻燃剂3：9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物，HCA，日本三光公司；Phosphorus-containing flame retardant 3: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, HCA, Japan Sanko Company;
含磷阻燃剂4：六苯氧基环三磷腈，威海金威；Phosphorus-containing flame retardant 4: Hexaphenoxycyclotriphosphazene, Weihai Kingway;
含磷阻燃剂5：1,3-亚苯基磷酸四(2,6-二甲苯基)酯，PX-200，日本大八化学工业株式会社；Phosphorus-containing flame retardant 5: 1,3-phenylene phosphate tetrakis (2,6-xylyl) ester, PX-200, Japan Daihachi Chemical Industry Co., Ltd.;
含磷阻燃剂6：有机次膦酸，FP-110，日本FUSHIMI；Phosphorus-containing flame retardant 6: organic phosphinic acid, FP-110, Japan FUSHIMI;
含磷阻燃剂7：间苯二酚双(二苯基磷酸酯)，Sol-DP，ICP-IP；Phosphorus-containing flame retardant 7: resorcinol bis(diphenyl phosphate), Sol-DP, ICP-IP;
磷酸锆：绵竹耀隆化工有限公司；Zirconium phosphate: Mianzhu Yaolong Chemical Co., Ltd.;
滑石粉1：HTPUltra5L，D50粒径为2μm，艾海薏米滑石粉；Talc powder 1: HTPUltra5L, D50 particle size is 2 μm, Aihai barley talc powder;
滑石粉2：SDC-9489，D50粒径为5μm，鑫达滑石粉；Talc powder 2: SDC-9489, D50 particle size is 5 μm, Xinda talc powder;
滑石粉3：AH-1250Y，D50粒径为10μm，艾海滑石粉；Talc powder 3: AH-1250Y, D50 particle size is 10μm, Aihai talc powder;
抗氧剂：抗氧剂1010，市售。Antioxidant: Antioxidant 1010, commercially available.
以下实施例和对比例中使用的抗氧剂均为同种物质。The antioxidants used in the following examples and comparative examples are all the same.
实施例1～23Examples 1-23
本发明所述阻燃聚碳酸酯组合物的实施例，实施例1～23的配方如表1所示。制备方法如下：按配比将各组分加入高混机中混合均匀；然后在双螺杆挤出机中熔融挤出，造粒，得到所述阻燃聚碳酸酯组合物；双螺杆挤出机的长径比40:1，螺杆温度280℃，转速为300r/min。Examples of the flame retardant polycarbonate composition of the present invention, the formulations of Examples 1 to 23 are shown in Table 1. The preparation method is as follows: add each component into a high mixer according to the proportion and mix them uniformly; then melt and extrude in a twin-screw extruder, and granulate to obtain the flame-retardant polycarbonate composition; The aspect ratio is 40:1, the screw temperature is 280°C, and the rotation speed is 300r/min.
对比例1～3Comparative example 1～3
对比例1～3为阻燃聚碳酸酯组合物，其配方如表1所示，制备方法与实施例1相同。Comparative Examples 1-3 are flame-retardant polycarbonate compositions, the formula of which is shown in Table 1, and the preparation method is the same as that of Example 1.
表1(重量份)Table 1 (parts by weight)
Figure PCTCN2022139284-appb-000001
Figure PCTCN2022139284-appb-000001
Figure PCTCN2022139284-appb-000002
Figure PCTCN2022139284-appb-000002
对实施例和对比例的性能进行测试，测试标准如下：The performance of embodiment and comparative example is tested, and test standard is as follows:
阻燃性测试：采用CZF-3型垂直燃烧测定仪按照UL94-2015对样品进行测试；Flame retardancy test: use CZF-3 vertical combustion tester to test the samples according to UL94-2015;
流动性：阿基米德螺旋线流动长度。螺旋界面为矩形，且宽度为5mm，厚度为1.4mm。将样品在280℃用阿基米德螺旋线模具注塑成型制件，其中注塑压力为50％，注塑速度为50％，制件取出后读取长度，记录10个样品的长度，并记录平均长度，单位为mm；Liquidity: The length of the flow of the Archimedes helix. The spiral interface is rectangular with a width of 5 mm and a thickness of 1.4 mm. The sample is injection-molded with an Archimedes spiral mold at 280°C, where the injection pressure is 50%, and the injection speed is 50%. After the part is taken out, the length is read, and the length of 10 samples is recorded, and the average length is recorded , the unit is mm;
缺口冲击强度：ASTM D256-2010；Notched impact strength: ASTM D256-2010;
测试结果记录在表2中。The test results are recorded in Table 2.
表2Table 2
项目project 螺旋线长度/mmHelix length/mm 阻燃t1+t2/sFlame retardant t1+t2/s 缺口冲击强度/J/mNotched impact strength/J/m
实施例1Example 1 488488 5.25.2 428428
实施例2Example 2 478478 6.36.3 403403
实施例3Example 3 475475 6.86.8 405405
实施例4Example 4 465465 6.86.8 398398
实施例5Example 5 451451 7.37.3 385385
实施例6Example 6 469469 6.76.7 386386
实施例7Example 7 459459 7.17.1 389389
实施例8Example 8 450450 7.37.3 384384
实施例9Example 9 450450 7.17.1 371371
实施例10Example 10 433433 7.77.7 380380
实施例11Example 11 432432 7.87.8 375375
实施例12Example 12 430430 7.57.5 373373
实施例13Example 13 438438 7.67.6 379379
实施例14Example 14 448448 7.47.4 382382
实施例15Example 15 440440 7.97.9 370370
实施例16Example 16 470470 6.86.8 403403
实施例17Example 17 522522 2.12.1 456456
实施例18Example 18 509509 4.24.2 433433
实施例19Example 19 511511 3.33.3 445445
实施例20Example 20 492492 5.15.1 430430
实施例21Example 21 490490 5.55.5 431431
实施例22Example 22 479479 5.85.8 432432
实施例23Example 23 475475 6.16.1 428428
对比例1Comparative example 1 420420 26.626.6 321321
对比例2Comparative example 2 386386 12.312.3 313313
对比例3Comparative example 3 346346 56.156.1 147147
由表2可知，实施例1～23所述聚碳酸酯组合物的螺旋线长度均大于430mm，具有良好的流动性；t1+t2都在10s内，满足UL94-2015的V-0要求；缺口冲击强度都高于370J/m，具有良好的抗冲击性能。对比例1中使用的含磷化合物为有机次膦酸，相比于本发明公开的磷腈阻燃剂、磷酸酯类阻燃剂、磷杂菲类阻燃剂，阻燃性能明显更差；对比例2仅添加含磷阻燃剂，阻燃性和抗冲击性能都很差；对比例3仅添加磷酸锆化合物，阻燃效果差，且流动性显著下降。It can be seen from Table 2 that the helix lengths of the polycarbonate compositions described in Examples 1 to 23 are all greater than 430mm, and have good fluidity; t1+t2 are all within 10s, meeting the V-0 requirements of UL94-2015; The impact strength is higher than 370J/m, with good impact resistance. The phosphorus-containing compound used in Comparative Example 1 is an organic phosphinic acid. Compared with the phosphazene flame retardants, phosphate ester flame retardants, and phosphaphenanthrene flame retardants disclosed in the present invention, the flame retardant performance is significantly worse; In Comparative Example 2, only phosphorus-containing flame retardants were added, and the flame retardancy and impact resistance were poor; in Comparative Example 3, only zirconium phosphate compounds were added, and the flame retardant effect was poor, and the fluidity decreased significantly.
对比实施例1～16与实施例17～23的测试结果可知，添加滑石粉的聚碳酸酯组合物的综合性能明显更好。其中，实施例17～23中实施例17～19的螺旋线长度均达到500mm以上，t1+t2均小于5s，缺口冲击强度均达到430J/m以上，兼具良好的流动性、阻燃性和抗冲击性能，该结果表明，粒径为1～3μm的滑石粉 和粒径为8～12μm的滑石粉以重量比1：(1～3)复配可以协同提升聚碳酸酯组合物的综合性能。Comparing the test results of Examples 1-16 with Examples 17-23, it can be seen that the comprehensive performance of the polycarbonate composition added with talc powder is obviously better. Among them, in Examples 17 to 23, the length of the helix in Examples 17 to 19 is more than 500mm, t1+t2 is less than 5s, and the notched impact strength is more than 430J/m, which has good fluidity, flame retardancy and Impact resistance, the results show that the combination of talc powder with a particle size of 1 to 3 μm and talc powder with a particle size of 8 to 12 μm at a weight ratio of 1: (1 to 3) can synergistically improve the overall performance of the polycarbonate composition .
另外，对比实施例1～3、16与实施例4～8的测试结果可知，含磷阻燃剂与磷酸锆的重量比为(5～8)：1时，聚碳酸酯组合物的综合性能更好；对比实施例4与实施例5的测试结果可知，虽然实施例5中含磷阻燃剂和磷酸锆的总重量份高于实施例4，但磷酸锆的占比过高，与含磷阻燃剂的重量比不在1：(3～10)的范围内，反而会影响聚碳酸酯组合物的阻燃性。对比实施例4、6、7与实施例9的测试结果可知，六氯环三磷腈和六苯氧基环三磷腈的重量比不在1：(1～4)的范围内时，综合性能会变差。对比实施例10～15与实施例4～8的测试结果可知，若只使用一种含磷化合物，聚碳酸酯的阻燃性会明显变差。In addition, comparing the test results of Examples 1-3, 16 with Examples 4-8, it can be seen that when the weight ratio of phosphorus-containing flame retardant to zirconium phosphate is (5-8):1, the overall performance of the polycarbonate composition Better; Comparing the test results of Example 4 and Example 5, it can be seen that although the total weight of phosphorus-containing flame retardant and zirconium phosphate in Example 5 is higher than that of Example 4, the proportion of zirconium phosphate is too high. The weight ratio of the phosphorus flame retardant is not in the range of 1:(3-10), which will affect the flame retardancy of the polycarbonate composition instead. Comparing the test results of Examples 4, 6, 7 and Example 9, it can be seen that when the weight ratio of hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene is not in the range of 1: (1～4), the overall performance will get worse. Comparing the test results of Examples 10-15 with Examples 4-8, it can be seen that if only one phosphorus-containing compound is used, the flame retardancy of polycarbonate will be obviously deteriorated.
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，但并不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solution of the present invention.

Claims (10)

  1. 一种阻燃聚碳酸酯组合物，其特征在于，包含如下重量份的成分：聚碳酸酯100份、含磷阻燃剂3～10份和磷酸锆1～5份；所述含磷阻燃剂为磷腈阻燃剂、磷酸酯类阻燃剂、磷杂菲类阻燃剂中的至少一种。A flame-retardant polycarbonate composition, characterized in that it comprises the following ingredients in parts by weight: 100 parts of polycarbonate, 3-10 parts of a phosphorus-containing flame retardant, and 1-5 parts of zirconium phosphate; the phosphorus-containing flame-retardant The agent is at least one of phosphazene flame retardants, phosphate ester flame retardants, and phosphaphenanthrene flame retardants.
  2. 如权利要求1所述的阻燃聚碳酸酯组合物，其特征在于，所述磷腈阻燃剂为六苯氧基环三磷腈、六氯环三磷腈、氨基环三磷腈、羟基环三磷腈、含双键环三磷腈中的至少一种；所述磷酸酯类阻燃剂为1,3-亚苯基磷酸四(2,6-二甲苯基)酯、磷酸三(2-氯丙基)酯、缩合磷酸酯、间苯二酚双(二苯基磷酸酯)中的至少一种；所述磷杂菲类阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物。Flame retardant polycarbonate composition as claimed in claim 1, is characterized in that, described phosphazene flame retardant is hexaphenoxycyclotriphosphazene, hexachlorocyclotriphosphazene, aminocyclotriphosphazene, hydroxyl At least one of cyclotriphosphazene and double bond-containing cyclotriphosphazene; the phosphoric acid ester flame retardant is 1,3-phenylene phosphate tetrakis (2,6-xylyl) ester, phosphoric acid tri( At least one of 2-chloropropyl) ester, condensed phosphoric acid ester, resorcinol bis(diphenyl phosphate); the phosphaphenanthrene flame retardant is 9,10-dihydro-9-oxygen Hetero-10-phosphaphenanthrene-10-oxide.
  3. 如权利要求2所述的阻燃聚碳酸酯组合物，其特征在于，所述含磷阻燃剂为六氯环三磷腈和六苯氧基环三磷腈重量比为1:(1～4)的复配物。Flame-retardant polycarbonate composition as claimed in claim 2, is characterized in that, described phosphorus-containing flame retardant is that hexachlorocyclotriphosphazene and hexaphenoxycyclotriphosphazene weight ratio are 1:(1～ 4) Compounds.
  4. 如权利要求1所述的阻燃聚碳酸酯组合物，其特征在于，所述含磷阻燃剂与磷酸锆的重量比为(3～10):1。The flame-retardant polycarbonate composition according to claim 1, wherein the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (3-10):1.
  5. 如权利要求4所述的阻燃聚碳酸酯组合物，其特征在于，所述含磷阻燃剂与磷酸锆的重量比为(5～8):1。The flame-retardant polycarbonate composition according to claim 4, wherein the weight ratio of the phosphorus-containing flame retardant to zirconium phosphate is (5-8):1.
  6. 如权利要求1所述的阻燃聚碳酸酯组合物，其特征在于，所述阻燃聚碳酸酯组合物还包含助剂0.1～1份；所述助剂为稳定剂、抗氧剂、阻燃剂、润滑剂、抗滴落剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的至少一种。The flame retardant polycarbonate composition according to claim 1, characterized in that, the flame retardant polycarbonate composition also comprises 0.1 to 1 parts of auxiliary agents; the auxiliary agents are stabilizers, antioxidants, At least one of fuel, lubricant, anti-dripping agent, release agent, plasticizer, filler, antistatic agent, antibacterial agent, and colorant.
  7. 如权利要求6所述的阻燃聚碳酸酯组合物，其特征在于，所述助剂为抗氧剂0.1～0.2份和填料0.2～0.8份的混合物。The flame retardant polycarbonate composition according to claim 6, characterized in that the auxiliary agent is a mixture of 0.1-0.2 parts of antioxidant and 0.2-0.8 parts of filler.
  8. 如权利要求7所述的阻燃聚碳酸酯组合物，其特征在于，所述填料为两种滑石粉的复配物，一种滑石粉的D50粒径为1～3μm，一种滑石粉的D50粒径为8～12μm，两者的重量比为1:(1～3)。The flame-retardant polycarbonate composition as claimed in claim 7, wherein the filler is a compound of two kinds of talcum powder, the D50 particle size of one kind of talcum powder is 1-3 μm, and the D50 particle size of one kind of talcum powder The D50 particle size is 8-12 μm, and the weight ratio of the two is 1:(1-3).
  9. 一种如权利要求1～8任一项所述的阻燃聚碳酸酯组合物的制备方法，其 特征在于，所述制备方法为：将各组分混合均匀，得到混合料，然后将混合料熔融挤出，造粒，得到所述阻燃聚碳酸酯组合物。A method for preparing the flame-retardant polycarbonate composition according to any one of claims 1 to 8, characterized in that, the preparation method is: mixing the components uniformly to obtain a mixture, and then mixing the mixture Melt extrusion and granulation to obtain the flame retardant polycarbonate composition.
  10. 一种如权利要求1～8任一项所述的阻燃聚碳酸酯组合物在汽车、电子、家电、建筑领域的应用。An application of the flame-retardant polycarbonate composition according to any one of claims 1 to 8 in the fields of automobiles, electronics, household appliances and construction.
PCT/CN2022/139284 2022-02-25 2022-12-15 Flame-retardant polycarbonate composition, preparation method therefor and application thereof WO2023160148A1 (en)

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