WO2022095384A1 - 一种高灼热丝聚甲醛组合物及其制备方法与应用 - Google Patents

一种高灼热丝聚甲醛组合物及其制备方法与应用 Download PDF

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WO2022095384A1
WO2022095384A1 PCT/CN2021/091428 CN2021091428W WO2022095384A1 WO 2022095384 A1 WO2022095384 A1 WO 2022095384A1 CN 2021091428 W CN2021091428 W CN 2021091428W WO 2022095384 A1 WO2022095384 A1 WO 2022095384A1
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flame retardant
polyoxymethylene composition
glow wire
composition according
lubricant
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French (fr)
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曹绍强
黄险波
叶南飚
陈锋
付学俊
丁超
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Kingfa Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts

Definitions

  • the invention belongs to the technical field of engineering plastics, and in particular relates to a high glow-filament polyoxymethylene composition and a preparation method and application thereof.
  • Polyoxymethylene (IUPAC named Polyoxymethylene, POM) is an engineering plastic with excellent performance, with hardness, strength and rigidity similar to metal, good self-lubrication, good resistance to a wide range of temperature and humidity. Fatigue, and elastic, in addition it has good chemical resistance.
  • POM is replacing some markets traditionally occupied by metals at a cost lower than many other engineering plastics, such as replacing zinc, brass, aluminum and steel to make many components, and has been widely used in electrical and electronic, machinery, instrumentation, Daily light industry, automobile, building materials, agriculture and other fields.
  • POM resin has a low oxygen index (14.9%), which makes it very easy to burn and has a phenomenon of melting and dripping; at the same time, the glow wire flammability index of POM resin is low, and the GWFI 2.0mm is only 600 °C, which cannot meet the Occasions with higher requirements for GWFI.
  • products such as double-ended connecting pins and installation cards in low-voltage electrical appliances require materials with high glow wire
  • GWFI 2.0mm requires 650 °C, and also requires materials with good mechanical properties, impact strength above 6.5KJ/m 2 , the tensile strength is above 25MPa.
  • POM resin is a highly crystalline polymer and has poor compatibility with other additives, adding a large amount of flame retardants will significantly reduce the mechanical properties of the material, especially the toughness.
  • the object of the present invention is to provide a high glow wire polyoxymethylene composition and its preparation method and application.
  • a high glow wire polyoxymethylene composition which comprises the following components in parts by weight: 40-60 parts of POM resin, 40-55 parts of flame retardant masterbatch, 0.5-2 parts of lubricant, 0.1-0.5 part of main antioxidant and 0.1-0.3 part of auxiliary antioxidant.
  • the flame retardant masterbatch includes the following components by weight: thermoplastic polyurethane elastomer (TPU) 21%-32%, ammonium polyphosphate (APP) 50%-70% and melamine cyanurate (MCA) 9%-18%, the Shore A hardness of the TPU is 75-95A.
  • TPU thermoplastic polyurethane elastomer
  • APP ammonium polyphosphate
  • MCA melamine cyanurate
  • TPU with Shore A hardness of 75-95A has good compatibility with POM resin, which can effectively improve the mechanical properties of the composition, especially the toughness.
  • the TPU is used to coat APP and MCA to form a flame retardant masterbatch, and then the flame retardant masterbatch is formed. Co-extrusion of fuel masterbatch and POM can effectively reduce the deterioration effect of APP and MCA on POM, thereby obtaining a composite material with better mechanical properties and higher glow wire flammability index.
  • TPU can also be used as a carbon-forming agent in the system of the present invention, and cooperate with APP to further improve the flame retardant performance of the composition.
  • the present invention has better flame retardant effect by coating APP and MCA at the same time, because MCA has a carbon-forming effect, and can play a better flame retardant modification effect in combination with APP.
  • the flame retardant masterbatch comprises the following components by weight: TPU 28%, APP 60% and MCA 12%. Using the flame retardant masterbatch of the formula, the comprehensive mechanical properties of the composition are better.
  • the phosphorus content of the APP is 27% to 32%.
  • the phosphorus content determines the improvement effect of APP on the glow wire performance of the composition; if the phosphorus content of the APP is low, it will lead to the need to add more APP to effectively improve the glow wire flammability index of the composition, but adding more APP will affect the glow wire flammability index of the composition.
  • the mechanical properties of the composition are adversely affected.
  • the phosphorus content of the APP is measured according to GB/T 10512-2008 "Determination of phosphorus content in nitrophosphate fertilizers by quinoline phosphomolybdate gravimetric method".
  • the POM resin has a melt index of 1 to 50 g/10min at 190° C. and a test condition of 2.16 kg, and a density of 1.38 to 1.43 g/cm 3 .
  • the lubricant is an amide lubricant; more preferably, at least one of erucamide, TAF (modified ethylene bis-fatty acid amide), and EBS B50 (N,N'-ethylene bis-stearamide) species; most preferably erucamide.
  • erucamide modified ethylene bis-fatty acid amide
  • EBS B50 N,N'-ethylene bis-stearamide
  • the main antioxidant is a hindered phenolic antioxidant, such as: BASF IRGANOX 245, bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid ] Tripolyethylene glycol, etc.
  • a hindered phenolic antioxidant such as: BASF IRGANOX 245, bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid ] Tripolyethylene glycol, etc.
  • the auxiliary antioxidant is selected from phosphite antioxidants (eg: tris(2,4-di-tert-butylphenyl) phosphite), thioether antioxidants (eg: pentaerythritol tetrakis) (3-lauryl thiopropionate)) at least one.
  • phosphite antioxidants eg: tris(2,4-di-tert-butylphenyl) phosphite
  • thioether antioxidants eg: pentaerythritol tetrakis
  • (3-lauryl thiopropionate) at least one.
  • the high glow wire polyoxymethylene composition of the present invention is suitable for low-voltage electrical appliances, and can meet the requirements of low-voltage electrical products with a GWFI of 2.0 mm reaching 650° C., impact strength of over 6.5 KJ/m 2 , and tensile strength of over 25 MPa.
  • the present invention also provides a preparation method of the high glow wire polyoxymethylene composition, which comprises the following steps:
  • the premix is melt-extruded, cooled and pelletized through a twin-screw extruder at 160-200° C. to obtain a polyoxymethylene composition.
  • the temperature of each barrel of the twin-screw extruder from the feeding port to the die head is: 150-170°C, 160-180°C, 160-180°C, 160-180°C, 170-190°C, 170- 190°C, 170 ⁇ 190°C, 180 ⁇ 200°C, 180 ⁇ 200°C and 180 ⁇ 200°C, the screw speed is 250 ⁇ 400r/min, the feed rate is 50 ⁇ 200kg/h, and the vacuum degree is -0.1 ⁇ 0MPa.
  • the invention also provides a preparation method of the flame retardant masterbatch, which comprises the following steps: adding TPU, APP and MCA together into a high-speed mixer and mixing for 2-5 minutes to obtain a premix; The twin-screw extruder is melt-extruded, cooled and pelletized at 160-200° C. to obtain the flame retardant master batch.
  • the beneficial effects of the present invention are as follows: the present invention adopts TPU with Shore A hardness of 75-95A to coat APP and MCA to form a flame retardant master batch, and then combine the flame retardant master batch with POM. Co-extrusion can effectively reduce the deterioration effect of flame retardant on POM, and obtain POM material with good mechanical properties and high glow wire flammability index at the same time.
  • the POM material is suitable for high glow wire and high mechanical properties. low-voltage electrical products, such as: double-ended connecting pins, installation cards.
  • Flame retardant masterbatch 1 is made of the following components by weight:
  • TPU KF-85AG (Hongyi Co., Ltd., Shore A hardness 85A): 28%, ammonium polyphosphate APP: 60%, and melamine cyanurate MCA: 12%.
  • the flame retardant masterbatch 2 is made of the following components by weight:
  • PolyBlend 1100-45A (AdvanSource Biomaterials Corp, 45A Shore A): 28%, ammonium polyphosphate APP: 60%, and melamine cyanurate MCA: 12%.
  • the flame retardant masterbatch 3 is made of the following components by weight:
  • Mirakutoran TPU E574 (Mirakutoran Corporation, Shore D hardness 74D): 28%, ammonium polyphosphate APP: 60%, and melamine cyanurate MCA: 12%.
  • ammonium polyphosphate APP and melamine cyanurate MCA used in the flame retardant master batch 1, the flame retardant master batch 2 and the flame retardant master batch 3 are the same products.
  • the phosphorus content of ammonium polyphosphate APP is 27% to 32%, which is purchased from Shouguang Weidong Chemical Co., Ltd., and the model is APP101 (the phosphorus content of APP101 is 27% to 29%).
  • APP102 produced by the company can also be used. (The phosphorus content of APP102 is 31% to 32%);
  • the purity of melamine cyanurate MCA is ⁇ 99.5%, and the pH value is 5.0 to 7.5. It was purchased from Sichuan Fine Chemical Research and Design Institute, and the model is MCA-01;
  • POM resin was purchased from Yunnan Yuntianhua Co., Ltd., model POM M270, melting index is 27g/10min (190°C/2.16kg), density is 1.4g/ cm3 ;
  • Amide lubricant erucamide, purchased from Croda Chem (Sichuan) Co., Ltd., model: CRODAMIDE ER-CH-MB-(SI), chemical name: (cis)-13-docosamide ;
  • Silicone lubricant MB50-002, purchased from Guangzhou Rongda Chemical Co., Ltd., silicone masterbatch;
  • Stearic acid lubricant CALCIUM STEARATE (BS-3818), purchased from Bailihe Chemical (Zhongshan) Co., Ltd., calcium stearate;
  • Stearic acid lubricant ZINC STEARATE (BS-2818), purchased from Zhongshan Huamingtai Chemical Material Technology Co., Ltd., zinc stearate;
  • the main antioxidant is bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid]tripolyethylene glycol, purchased from Guangzhou Aoying Trading Co., Ltd. , the model is IRGANOX 245;
  • the auxiliary antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, purchased from Foshan Yuansheng Chemical Co., Ltd., the model is SONOX 168.
  • the preparation method of the flame retardant masterbatch is as follows: adding TPU, APP and MCA together in a high-speed mixer and mixing for 2 to 5 minutes to obtain a premix; After discharging, cooling and granulating, the flame retardant masterbatch is obtained.
  • the temperature of each barrel of the twin-screw extruder from the feeding port to the die head is: 150-170°C, 160-180°C, 160-180°C, 160-180°C, 170-190°C, 170-190°C , 170 ⁇ 190°C, 180 ⁇ 200°C, 180 ⁇ 200°C, 180 ⁇ 200°C, the screw speed is 250 ⁇ 400 rpm, the feeding amount is 50 ⁇ 200kg/h, and the vacuum degree is -0.1 ⁇ 0MPa.
  • Glow wire GWFI test standard IEC 60695-2-12:2014, sample thickness 2.0mm;
  • Extrusion granulation Observe the particles during the extrusion process. The surface of the normal particles is intact, there are 1 to 2 vacuum holes in the middle, and there is no crushing; the foamed particles are expanded or crushed.
  • the temperature of each screw barrel of the twin-screw extruder from the feeding port to the die head is: 150-170 °C, 160-180 °C, 160-180 °C, 160-180 °C, 170-190 °C °C, 170 ⁇ 190°C, 170 ⁇ 190°C, 180 ⁇ 200°C, 180 ⁇ 200°C and 180 ⁇ 200°C, the screw speed is 250 ⁇ 400r/min, the feeding amount is 50 ⁇ 200kg/h, the vacuum degree is - 0.1 ⁇ 0MPa.
  • Example 7 without adding flame retardant masterbatch, the tensile strength of the composition is improved compared with Example 3, but the notched impact strength is significantly reduced, and the GWFI2.0mm is only 600 ° C, indicating that the present invention
  • the addition of the flame retardant masterbatch can effectively improve the glow wire flammability index of the composition, and at the same time, because the flame retardant masterbatch contains the TPU with the hardness of the present invention, it can significantly increase the toughness of the composition, but no matter what kind of TPU
  • the addition will reduce the tensile strength of the composition, while the composition obtained with the formulation of the present invention has higher glow wire flammability index and toughness, and the tensile strength can also meet the requirements of low-voltage electrical appliances.
  • amide lubricants such as erucamide have a good stabilizing effect on the system, which can ensure the smooth progress of the extrusion process, and the extruded particles are normal, but if the amide lubricant is Replacing the lubricant with other types of lubricants such as silicone lubricant MB50-002, stearic acid lubricant CALCIUM STEARATE (BS-3818), or ZINC STEARATE (BS-2818) will lead to foaming of extruded particles. Serious, and stearic acid lubricants can also discolor the system.
  • test groups 1 to 3 in Table 2.
  • the flame retardant master batches were prepared according to the weight percentage formulas of test groups 1 to 3, respectively, and then the polyoxymethylene composition was prepared according to the formula and method of Example 1, and the flame retardant master batches of each test group were tested.
  • the performance of the polyoxymethylene composition the results are shown in Table 3.
  • Test group 1 Test group 2
  • Test group 3 GWFI 2.0mm 650 650
  • the change of the component distribution ratio in the flame retardant master batch of the present invention will have an impact on the mechanical properties of the composition, and the comprehensive mechanical properties of the composition added with the flame retardant master batch of test group 2 are better .

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Abstract

一种高灼热丝聚甲醛组合物，其包括如下重量份的组分：POM树脂40～60份、阻燃剂母粒40～55份、润滑剂0.5～2份、主抗氧剂0.1～0.5份和辅抗氧剂0.1～0.3份；所述阻燃剂母粒包括如下重量百分含量的组分：热塑性聚氨酯弹性体21％～32％、聚磷酸铵50％～70％和三聚氰胺氰尿酸盐9％～18％，所述热塑性聚氨酯弹性体的邵氏A硬度为75～95A。

Description

一种高灼热丝聚甲醛组合物及其制备方法与应用 技术领域
本发明属于工程塑料技术领域，具体涉及一种高灼热丝聚甲醛组合物及其制备方法与应用。
背景技术
聚甲醛(IUPAC命名Polyoxymethylene，POM)是一种性能优良的工程塑料，具有类似金属的硬度、强度和钢性，在很宽的温度和湿度范围内都具有很好的自润滑性、良好的耐疲劳性，并富于弹性，此外它还有较好的耐化学品性。目前，POM以低于其他许多工程塑料的成本，正在替代一些传统上被金属所占领的市场，如替代锌、黄铜、铝和钢制作许多部件，已经广泛应用于电子电气、机械、仪表、日用轻工、汽车、建材、农业等领域。
然而，POM树脂具有较低的氧指数(14.9％)，导致其非常容易燃烧，且有熔融滴落现象；同时，POM树脂的灼热丝可燃性指数较低，GWFI 2.0mm只有600℃，无法满足对GWFI要求更高的场合。比如，低压电器中的双头连接销、安装卡等产品要求材料有高的灼热丝，GWFI 2.0mm要求650℃，同时还要求材料有较好的力学性能，冲击强度在6.5KJ/m 2以上，拉伸强度在25MPa以上。而由于POM树脂为高结晶性的聚合物，与其他添加剂的相容性差，大量添加阻燃剂会使得材料的力学性能明显下降，尤其是韧性。
因此，如何获得同时具有高灼热丝和力学性能较好的POM材料已成为目前亟需解决的技术问题。
发明内容
为解决上述现有技术中存在的不足之处，本发明的目的在于提供一种高灼热丝聚甲醛组合物及其制备方法与应用。
为达到其目的，本发明所采用的技术方案为：一种高灼热丝聚甲醛组合物， 其包括如下重量份的组分：POM树脂40～60份、阻燃剂母粒40～55份、润滑剂0.5～2份、主抗氧剂0.1～0.5份和辅抗氧剂0.1～0.3份。
优选地，所述阻燃剂母粒包括如下重量百分含量的组分：热塑性聚氨酯弹性体(TPU)21％～32％、聚磷酸铵(APP)50％～70％和三聚氰胺氰尿酸盐(MCA)9％～18％，所述TPU的邵氏A硬度为75～95A。
邵氏A硬度为75～95A的TPU与POM树脂的相容性好，能有效提高组合物的力学性能，尤其是韧性，以该TPU包覆APP和MCA形成阻燃剂母粒，再将阻燃剂母粒与POM进行共挤出，可有效减小APP和MCA对POM的劣化作用，从而获得具有较好力学性能和较高灼热丝可燃性指数的组合物材料。同时，由于聚磷酸铵在空气中受热后首先会氧化成P 2O 5，继而生成磷酸、偏磷酸和焦磷酸，而这些物质可使聚氨酯脱水成炭形成炭正离子，因炭质层不易燃，并会覆盖和围绕聚合物，从而隔绝火焰和空气中的氧，起到阻燃作用，因此TPU在本发明体系中还可作为成炭剂，与APP配合进一步提高组合物的阻燃性能。
研究发现，若TPU的硬度过大，因其具有较低的伸长率和韧性，以其作为包覆层，会导致组合物的力学性能较差，尤其是韧性。若TPU的硬度过小，因其具有较低的刚性，以其作为包覆层，虽然会增加组合物的韧性，但会导致组合物的拉伸强度大幅下降。
此外，相比于只包覆APP，本发明同时包覆APP和MCA具有更好的阻燃效果，这是由于MCA具有成炭作用，与APP配合可发挥更优的阻燃改性效果。
优选地，所述阻燃剂母粒包括如下重量百分含量的组分：TPU 28％、APP 60％和MCA 12％。使用该配方的阻燃剂母粒，组合物的综合力学性能较好。
优选地，所述APP的磷含量为27％～32％。磷含量决定APP对组合物灼热丝性能的改善效果；若APP的磷含量较低，会导致需要添加更多的APP才能有效提高组合物的灼热丝可燃性指数，但添加更多的APP会对组合物的力学性能产生不利影响。本发明中，所述APP的磷含量根据GB/T 10512-2008《硝酸磷肥中磷含量的测定磷钼酸喹啉重量法》进行测定。
优选地，所述POM树脂在190℃、2.16kg测试条件下的熔融指数为1～50g/10min；密度为1.38～1.43g/cm 3。
优选地，所述润滑剂为酰胺类润滑剂；更优选为芥酸酰胺、TAF(改性乙撑双脂肪酸酰胺)、EBS B50(N,N'-乙撑双硬脂酰胺)中的至少一种；最优选为芥酸酰胺。研究发现，在低甲醛低气味POM体系(重量份配方组成为：POM树脂97.2份、酰胺类润滑剂2份、主抗氧剂IRGANOX 245 0.3份、辅抗氧剂SONOX 168 0.2份和亚硫酸氢钠0.3份)中，以芥酸酰胺作为润滑剂时，组合物具有更高的稳定性。经实验证实，润滑剂添加量均为2重量份的情况下，加入芥酸酰胺的组合物的甲醛释放量为1ppm左右(VDA275)，而加入TAF或EBS B50的组合物的甲醛释放量在3ppm左右(VDA275)，因此，本发明优选采用芥酸酰胺作为润滑剂。
优选地，所述主抗氧剂为受阻酚类抗氧剂，如：巴斯夫IRGANOX 245、二[3-(1,1-二甲基乙基)-4-羟基-5-甲基苯丙酸]三聚乙二醇等。
优选地，所述辅抗氧剂选自亚磷酸酯类抗氧剂(如：亚磷酸三(2,4-二叔丁基苯基)酯)、硫醚类抗氧剂(如：季戊四醇四(3-月桂基硫代丙酸酯))中的至少一种。
本发明的高灼热丝聚甲醛组合物适用于低压电器中，能满足低压电器产品所需的GWFI 2.0mm达到650℃，冲击强度在6.5KJ/m 2以上，拉伸强度在25MPa以上的要求。
本发明还提供了一种所述高灼热丝聚甲醛组合物的制备方法，其包括如下步骤：
(1)将POM树脂、阻燃剂母粒、润滑剂、主抗氧化和辅抗氧剂一起加入高速混合机中混合2～5min，得到预混料；
(2)将预混料经双螺杆挤出机在160～200℃下熔融挤出、冷却、造粒，得到聚甲醛组合物。
其中，所述双螺杆挤出机由加料口到机头的各螺筒温度分别为：150～170℃、160～180℃、160～180℃、160～180℃、170～190℃、170～190℃、170～190℃、 180～200℃、180～200℃和180～200℃，螺杆转速为250～400r/min，喂料量为50～200kg/h，真空度为-0.1～0MPa。
本发明还提供了一种所述阻燃剂母粒的制备方法，其包括如下步骤：将TPU、APP和MCA一起加入高速混合机中混合2～5min，得到预混料；将预混料经双螺杆挤出机在160～200℃下熔融挤出、冷却、造粒，得到所述阻燃剂母粒。
与现有技术相比，本发明的有益效果为：本发明采用了邵氏A硬度为75～95A的TPU包覆APP和MCA、形成阻燃剂母粒，再将阻燃剂母粒与POM进行共挤出，有效减小了阻燃剂对POM的劣化作用，获得同时具有较好力学性能和较高灼热丝可燃性指数的POM材料，该POM材料适用于要求高灼热丝和高力学性能的低压电器产品，如：双头连接销、安装卡。
具体实施方式
下面将结合实施例对本发明的技术方案作进一步描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例和对比例所用的原料均可通过市售购买获得，其中：
1、阻燃剂母粒①由如下重量百分含量的组分制成：
TPU KF-85AG(虹溢股份有限公司，邵氏A硬度85A)：28％、聚磷酸铵APP：60％、以及三聚氰胺氰尿酸盐MCA：12％。
2、阻燃剂母粒②由如下重量百分含量的组分制成：
PolyBlend 1100-45A(AdvanSource Biomaterials Corp，邵氏A硬度45A)：28％、聚磷酸铵APP：60％、以及三聚氰胺氰尿酸盐MCA：12％。
3、阻燃剂母粒③由如下重量百分含量的组分制成：
Mirakutoran TPU E574(Mirakutoran公司，邵氏D硬度74D)：28％、聚磷酸铵APP：60％、以及三聚氰胺氰尿酸盐MCA：12％。
阻燃剂母粒①、阻燃剂母粒②和阻燃剂母粒③使用的聚磷酸铵APP和三聚氰胺氰尿酸盐MCA为相同产品。
其中，聚磷酸铵APP的磷含量为27％～32％，购自寿光卫东化工有限公司，型号为APP101(APP101的磷含量为27％～29％)，此外还可采用该公司生产的APP102(APP102的磷含量为31％～32％)；
三聚氰胺氰尿酸盐MCA的纯度≥99.5％，pH值为5.0～7.5，购自四川省精细化工研究设计院，型号为MCA-01；
4、POM树脂购自云南云天化股份有限公司，型号POM M270，熔指为27g/10min(190℃/2.16kg)，密度为1.4g/cm 3；
5、酰胺类润滑剂：芥酸酰胺，购自禾大西普化学(四川)有限公司，型号：CRODAMIDE ER-CH-MB-(SI)，化学名：(顺)-13-二十二烯酰胺；
6、硅酮类润滑剂：MB50-002，购自广州融大化工有限公司，硅酮母粒；
7、硬脂酸类润滑剂：CALCIUM STEARATE(BS-3818)，购自百利合化工(中山)有限公司，硬脂酸钙；
8、硬脂酸类润滑剂：ZINC STEARATE(BS-2818)，购自中山市华明泰化工材料科技有限公司，硬脂酸锌；
9、主抗氧剂为二[3-(1,1-二甲基乙基)-4-羟基-5-甲基苯丙酸]三聚乙二醇，购自广州市奥莹贸易有限公司，型号为IRGANOX 245；
10、辅抗氧剂为亚磷酸三(2,4-二叔丁基苯基)酯，购自佛山市沅胜化工有限公司，型号为SONOX 168。
阻燃剂母粒的制备方法为：将TPU、APP和MCA一起加入高速混合机中混合2～5min，得到预混料；将预混料经双螺杆挤出机在160～200℃下熔融挤出、冷却、造粒，即得阻燃剂母粒。其中，双螺杆挤出机由加料口到机头的各螺筒温度分别为：150～170℃、160～180℃、160～180℃、160～180℃、170～190℃、170～190℃、170～190℃、180～200℃、180～200℃、180～200℃，螺杆转速为250～400转/分钟，喂料量为50～200kg/h，真空度为-0.1～0MPa。
性能测试标准：
灼热丝GWFI：测试标准IEC 60695-2-12:2014，样板厚度2.0mm；
拉伸强度：测试标准ISO 527-2:2012，测试速度50mm/min；
缺口冲击强度：测试标准ISO 180:2013，摆锤能量2.75J；
挤出造粒性：在挤出过程中观察粒子情况，正常粒子的表面完好，中间有 1～2个真空眼，无粉碎；发泡的粒子为膨胀或碎末状。
一、实施例1～4和对比例1～10的聚甲醛组合物的配方见表1，制备方法如下：
(1)将原料组分一起加入高速混合机中混合2～5min，得到预混料；
(2)将预混料从主喂口加入双螺杆挤出机中，玻璃纤维从侧喂口加入双螺杆挤出机中，在160～200℃下熔融挤出、冷却、造粒，得到聚甲醛组合物；其中，所述双螺杆挤出机由加料口到机头的各螺筒温度分别为：150～170℃、160～180℃、160～180℃、160～180℃、170～190℃、170～190℃、170～190℃、180～200℃、180～200℃和180～200℃，螺杆转速为250～400r/min，喂料量为50～200kg/h，真空度为-0.1～0MPa。
将实施例1～4和对比例1～10的聚甲醛组合物按照上述性能测试标准制备成样品测试相关性能，测试结果见表1。
表1
Figure PCTCN2021091428-appb-000001
Figure PCTCN2021091428-appb-000002
表1(续)
组分(重量份) 对比例8 对比例9 对比例10
POM 53.5 53.5 53.5
阻燃剂母粒① 45 45 45
MB50-002 1 - -
CALCIUMSTEARATE(BS-3818) - 1 -
ZINCSTEARATE(BS-2818) - - 1
主抗氧剂 0.3 0.3 0.3
辅抗氧剂 0.2 0.2 0.2
GWFI2.0mm 650 650 650
拉伸强度MPa 25.5 22.4 21.6
缺口冲击强度KJ/m 2 3.5 3.2 3.4
挤出造粒性 发泡 发泡且变色 发泡且变色
注：表中“-”表示未添加该原料。
结果分析：
比较实施例1～4和对比例1～2可看出，本发明配方体系中，POM和阻燃剂母粒的添加量会对组合物的力学性能和灼热丝可燃性指数产生影响。以本发明提供的添加量范围制得的组合物具有较好的力学性能，拉伸强度和缺口冲击强度均较高，且GWFI 2.0mm达到650℃。而若POM的占比过大，且阻燃剂母粒的占比过小时，组合物的GWFI 2.0mm仅为600℃，且韧性较低。若POM的占比过小，且阻燃剂母粒的占比过大时，组合物的拉伸强度显著下降。
比较实施例3、对比例3～4和对比例7可看出，若将阻燃剂母粒的包覆层TPU换成硬度较小的TPU(即对比例3)时，虽然组合物的韧性(缺口冲击强 度)有所提高，但其拉伸强度显著下降，无法达到低压电器的力学性能要求。若将阻燃剂母粒的包覆层TPU换成硬度较大的TPU(即对比例4)时，组合物的拉伸强度和缺口冲击强度均显著下降。而不加入阻燃剂母粒的对比例7中，组合物的拉伸强度相较于实施例3有所提高，但缺口冲击强度显著下降，GWFI2.0mm也仅有600℃，说明，本发明阻燃剂母粒的加入可有效提高组合物的灼热丝可燃性指数，同时由于阻燃剂母粒含有本发明所述硬度的TPU，因此可显著增加组合物的韧性，但不管何种TPU的加入都会降低组合物的拉伸强度，而以本发明配方获得的组合物具有较高的灼热丝可燃性指数和韧性，且拉伸强度也能达到低压电器的要求。
比较实施例2和对比例5～6可看出，若将TPU、APP和MCA直接加入组合物中而不进行预包覆处理，会导致组合物的力学性能显著下降，尤其是韧性，这是由于APP和MCA对POM的裂化作用而导致的。
比较实施例2和对比例8～10可看出，芥酸酰胺等酰胺类润滑剂对于体系具有很好的稳定作用，可确保挤出过程顺利进行，并且挤出的粒子正常，但如果将酰胺类润滑剂替换成硅酮类润滑剂MB50-002、硬脂酸类润滑剂CALCIUM STEARATE(BS-3818)、或ZINC STEARATE(BS-2818)等其它类型的润滑剂，会导致挤出粒子发泡严重，并且硬脂酸类润滑剂还会使体系颜色变色。
二、探究阻燃剂母粒的组分配比对组合物性能的影响，设置了表2的试验组1～3。分别按照试验组1～3的重量百分含量配方制备阻燃剂母粒，然后按照实施例1的配方和方法制备聚甲醛组合物，检测用各试验组的阻燃剂母粒所制得的聚甲醛组合物的性能，结果如表3所示。
表2
组分，％ 试验组1 试验组2 试验组3
TPU KF-85AG 32 28 21
APP101 50 60 70
MCA-01 18 12 9
表3
组分 试验组1 试验组2 试验组3
GWFI 2.0mm 650 650 650
拉伸强度MPa 35.8 41.2 36.2
缺口冲击强度KJ/m 2 8.9 8.4 7.1
从表3可看出，本发明阻燃剂母粒中的组分配比改变会对组合物的力学性能产生影响，而加入试验组2的阻燃剂母粒的组合物的综合力学性能较优。
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)

  1. 一种高灼热丝聚甲醛组合物，其特征在于，包括如下重量份的组分：POM树脂40～60份、阻燃剂母粒40～55份、润滑剂0.5～2份、主抗氧剂0.1～0.5份和辅抗氧剂0.1～0.3份；所述阻燃剂母粒包括如下重量百分含量的组分：热塑性聚氨酯弹性体21％～32％、聚磷酸铵50％～70％和三聚氰胺氰尿酸盐9％～18％，所述热塑性聚氨酯弹性体的邵氏A硬度为75～95A。
  2. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述阻燃剂母粒包括如下重量百分含量的组分：热塑性聚氨酯弹性体28％、聚磷酸铵60％和三聚氰胺氰尿酸盐12％。
  3. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述APP的磷含量为27％～32％。
  4. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述POM树脂在190℃、2.16kg测试条件下的熔融指数为1～50g/10min；密度为1.38～1.43g/cm 3。
  5. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述润滑剂为酰胺类润滑剂。
  6. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述润滑剂为芥酸酰胺、TAF、EBS B50中的至少一种。
  7. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述主抗氧剂为受阻酚类抗氧剂。
  8. 如权利要求1所述的高灼热丝聚甲醛组合物，其特征在于，所述辅抗氧剂选自亚磷酸酯类抗氧剂、硫醚类抗氧剂中的至少一种。
  9. 如权利要求1～8任一项所述的高灼热丝聚甲醛组合物的制备方法，其特征在于，包括如下步骤：
    (1)将POM树脂、阻燃剂母粒、润滑剂、主抗氧化和辅抗氧剂一起加入 高速混合机中混合2～5min，得到预混料；
    (2)将预混料经双螺杆挤出机在160～200℃下熔融挤出、冷却、造粒，得到聚甲醛组合物；
    所述阻燃剂母粒的制备方法，包括如下步骤：将热塑性聚氨酯弹性体、聚磷酸铵和三聚氰胺氰尿酸盐一起加入高速混合机中混合2～5min，得到预混料；将预混料经双螺杆挤出机在160～200℃下熔融挤出、冷却、造粒，得到所述阻燃剂母粒。
  10. 如权利要求1～8任一项所述的高灼热丝聚甲醛组合物在低压电器中的应用。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260700A (zh) * 2022-08-26 2022-11-01 万敬新材料(上海)有限公司 低温增韧聚甲醛组合物及其制造方法
CN115260739A (zh) * 2022-08-08 2022-11-01 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN115304843A (zh) * 2022-08-26 2022-11-08 扬州绿宝人造草坪有限公司 一种高强度阻燃人造草丝

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321988B (zh) * 2020-11-09 2022-05-06 金发科技股份有限公司 一种高灼热丝聚甲醛组合物及其制备方法与应用
CN114507441B (zh) * 2021-12-24 2025-04-29 金发科技股份有限公司 一种聚酰胺复合材料及其制备方法和应用
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1810881A (zh) * 2006-03-08 2006-08-02 四川大学 聚氨酯基复合阻燃剂阻燃聚甲醛材料的制备方法
CN104312085A (zh) * 2014-10-30 2015-01-28 山西新华化工有限责任公司 阻燃耐腐蚀防毒面具罐接头座pom塑料配方及制备方法
CN110607066A (zh) * 2019-10-09 2019-12-24 江苏万纳普新材料科技有限公司 一种聚甲醛改性专用无卤阻燃增效功能母粒及其制备方法
CN111635613A (zh) * 2020-05-11 2020-09-08 天津金发新材料有限公司 一种超韧、耐磨pom/tpu组合物及其制备方法
CN112321988A (zh) * 2020-11-09 2021-02-05 金发科技股份有限公司 一种高灼热丝聚甲醛组合物及其制备方法与应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3789489B2 (ja) * 1992-04-04 2006-06-21 三菱瓦斯化学株式会社 耐衝撃性ポリアセタール組成物の製造方法
CN103435966A (zh) * 2012-12-19 2013-12-11 安徽科聚新材料有限公司 一种聚甲醛材料及其制备方法
CN106366558A (zh) * 2016-09-30 2017-02-01 无锡市明盛强力风机有限公司 一种工程塑料材料及制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1810881A (zh) * 2006-03-08 2006-08-02 四川大学 聚氨酯基复合阻燃剂阻燃聚甲醛材料的制备方法
CN104312085A (zh) * 2014-10-30 2015-01-28 山西新华化工有限责任公司 阻燃耐腐蚀防毒面具罐接头座pom塑料配方及制备方法
CN110607066A (zh) * 2019-10-09 2019-12-24 江苏万纳普新材料科技有限公司 一种聚甲醛改性专用无卤阻燃增效功能母粒及其制备方法
CN111635613A (zh) * 2020-05-11 2020-09-08 天津金发新材料有限公司 一种超韧、耐磨pom/tpu组合物及其制备方法
CN112321988A (zh) * 2020-11-09 2021-02-05 金发科技股份有限公司 一种高灼热丝聚甲醛组合物及其制备方法与应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XIE DAI-YI, LIU YUAN, WANG QI: "Study on Flame Retardation of POM by Melamine Cyanurate/TPU Composite", CHINA PLASTICS INDUSTRY, vol. 34, no. 4, 30 April 2006 (2006-04-30), pages 17 - 19, XP009536565, ISSN: 1005-5770 *
XIE DAIYI: "Studies on TPU/MCA and TPU/IFR Composites Flame Retardant POM", CHINESE DOCTORAL DISSERTATIONS & MASTER'S THESES FULL-TEXT DATABASE, GRADUATE SCHOOL OF PEKING UNION MEDICAL COLLEGE, CN, no. 3, 15 March 2007 (2007-03-15), CN , XP055927607, ISSN: 1671-6779 *
YUAN LIU, MEIFANG LIU, DAIYI XIE, QI WANG: "Thermoplastic Polyurethane-Encapsulated Melamine Phosphate Flame Retardant Polyoxymethylene", POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING, vol. 47, no. 3, 1 March 2008 (2008-03-01), US , pages 330 - 334, XP009536566, ISSN: 0360-2559, DOI: 10.1080/03602550701870099 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260739A (zh) * 2022-08-08 2022-11-01 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN115260739B (zh) * 2022-08-08 2023-08-15 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN115260700A (zh) * 2022-08-26 2022-11-01 万敬新材料(上海)有限公司 低温增韧聚甲醛组合物及其制造方法
CN115304843A (zh) * 2022-08-26 2022-11-08 扬州绿宝人造草坪有限公司 一种高强度阻燃人造草丝
CN115304843B (zh) * 2022-08-26 2023-08-04 扬州绿宝人造草坪有限公司 一种高强度阻燃人造草丝

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