WO2021258674A1 - Polyester material having high glow-wire ignition temperature resistance and preparation method therefor - Google Patents

Polyester material having high glow-wire ignition temperature resistance and preparation method therefor Download PDF

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WO2021258674A1
WO2021258674A1 PCT/CN2020/136319 CN2020136319W WO2021258674A1 WO 2021258674 A1 WO2021258674 A1 WO 2021258674A1 CN 2020136319 W CN2020136319 W CN 2020136319W WO 2021258674 A1 WO2021258674 A1 WO 2021258674A1
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parts
ignition temperature
polyester material
glass fiber
high glow
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PCT/CN2020/136319
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French (fr)
Chinese (zh)
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朱文
黄险波
叶南飚
莫文杰
姚华侠
龚德君
陈锐
付学俊
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金发科技股份有限公司
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Publication of WO2021258674A1 publication Critical patent/WO2021258674A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08K3/32—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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of polymer material modification, in particular to a polyester material with high glow wire resistance to ignition temperature and a preparation method thereof.
  • Polybutylene terephthalate PBT and polyethylene terephthalate PET are two thermoplastic polyester materials commonly used as functional structural parts in the electronic and electrical industry. Due to crystallization and linear saturation, they have excellent electrical properties. Performance, mechanical strength and processability, the modified polyester has been widely used in the fields of electronics, electrical appliances, home appliances, and automobiles. The safety requirements of materials are becoming more and more stringent. In addition to meeting the UL94 flame retardant rating in many industries, the glow-wire ignition temperature (GWIT) requirements in the IEC60695 standard must also be enforced.
  • GWIT glow-wire ignition temperature
  • GWIT For plastics used in electrical appliances that are unsupervised for a long time
  • the component standard proposes that GWIT must meet ⁇ 775°C, and now with the realization of more and more functions of electronic devices, GWIT requirements for specific components such as connectors, relay housings, circuit breaker housings, etc., must reach 850°C or above.
  • the flame-retardant glass fiber reinforced polyester material can obtain a higher GWIT at a thinner thickness level (such as 0.75mm or less) and a higher thickness level (such as 3.0mm or above), but In the middle thickness, such as 1.0 ⁇ 2.0mm, the GWIT is lower.
  • the same flame retardant material can reach 700°C or 725°C at a thickness of 1.5mm, but can reach 750°C or 775°C at a thickness of 3.0mm or 0.75mm.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a polyester material with high glow-wire resistance.
  • the present invention uses halogenated flame retardant and nitrogen-phosphorus compound synergist to effectively combine without antimony compound to obtain glass fiber reinforced flame-retardant polyester material.
  • the polyester material has excellent mechanical properties, a variety of colors and The wall thickness is between 1.0-2.0mm and the GWIT reaches 875°C or above.
  • the technical solution adopted by the present invention is: a polyester material with high glow wire ignition temperature resistance, including the following components by weight: 25-40 parts of polyester resin, 25- 40 parts of alkali-free glass fiber 40 parts, 18-30 parts of brominated flame retardant, 3-8 parts of nitrogen-containing smoke suppressant and 2-10 parts of phosphate flame retardant synergist; the alkali-free glass fiber is treated with coupling agent Alkali-free glass fiber.
  • the brominated flame retardant, the nitrogen-containing smoke suppressant and the phosphorus-containing flame retardant synergist of the present application can play a better synergistic effect within the above-mentioned content range, so that the polyester material has better flame retardancy Effect, high mechanical strength, high resistance to high glow wire ignition temperature.
  • the raw fiber of glass fiber is coated with a sizing agent containing silane coupling agent during the drawing process, then dried and pelletized to obtain alkali-free glass fiber treated with coupling agent; glass fiber and polyester resin treated with coupling agent
  • the interface is tightly bonded, which greatly contributes to the improvement of the mechanical strength of the composite material.
  • the diameter of the alkali-free glass fiber is 10-13 ⁇ m.
  • the polyester resin is at least one of polybutylene terephthalate and polyethylene terephthalate.
  • the brominated flame retardant is brominated triazine.
  • Bromotriazine has a higher bromine content than other ordinary bromine flame retardants and contains nitrogen. Its flame retardant mechanism is de-endothermic decomposition type, and its flame retardant efficiency is higher.
  • the nitrogen-containing smoke suppressant is at least one of melamine cyanurate and melamine polyphosphate.
  • the melamine-based nitrogen-containing smoke suppressant and the phosphorus-based flame retardant have a good coordination flame retardant effect, which can achieve the characteristics of low dosage, good flame retardant effect and low smoke emission.
  • the phosphate flame retardant synergist is bisphenyl phosphate.
  • the polyester material with high glow-wire resistance to ignition temperature further contains the following components in parts by weight: 0-8 parts of toughening agent and 0-5 parts of processing aid.
  • the toughening agent is at least one of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate binary copolymer, and ethylene-butyl acrylate binary copolymer
  • the processing aid includes a composite antioxidant system, a lubricant and a pigment, the composite antioxidant system is composed of hindered phenolic antioxidants, phosphite antioxidants, and organic sulfur antioxidants, the lubricating The agent is at least one of an aliphatic carboxylate lubricant and a polyolefin lubricant.
  • the present invention also provides a method for preparing the polyester material with high glow wire resistance to ignition temperature, and the method is:
  • the polyester resin pre-dry the polyester resin at 120-140°C for 4-6 hours, then mix the dried polyester resin with other ingredients except for the alkali-free glass fiber, and then send the mixture into In the twin-screw extruder, the alkali-free glass fiber is added to the side feeding port of the twin-screw extruder at the same time. After extrusion, drawing, cooling, pelletizing, drying, and packaging, a polymer with high glow wire ignition temperature resistance is obtained. Ester material.
  • the feed of the twin-screw extruder is 450-800kg/hour; the temperature of each section of the twin-screw extruder from the feeding port to the die is 220-230°C, 230-240 °C, 230-240°C, 240-250°C, 250-260°C, 240-250°C, 240-250°C, 230-240°C, 230-240°C, 230-240°C, the screw speed of the twin screw extruder is 250 ⁇ 400rpm.
  • the antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow-wire ignition temperature resistance obtained by the present invention has UL-94 standard V-0 level of flame retardancy, and is within 1.0-2.0mm
  • the GWIT in the thickness can reach 875°C or above;
  • the antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow wire ignition temperature resistance obtained by the present invention has a tensile strength of more than 100MPa and a notched impact strength of more than 7.5kJ/m 2 (ISO standard);
  • the antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow wire ignition temperature resistance obtained in the present invention does not contain antimony and its compounds, and avoids the possibility of heavy metals exceeding the standard caused by antimony compounds in the management and control of environmental substances Problems such as the use of antimony compounds may cause occupational diseases and other risks.
  • A1 PBT resin, Changchun 1100-211M, Taiwan;
  • A2 PET resin, Yizheng Chemical Fiber FG600;
  • E1 Bisphenyl phosphate
  • WSFR-PX220 hydroquinone bis(diphenyl phosphate)), Wansheng;
  • E2 Phenyl phosphate
  • WSFR-RDP resorcinol (diphenyl phosphate)
  • Wansheng Phenyl phosphate
  • F1 Ethylene-acrylate-glycidyl methacrylate terpolymer, grade PTW (DuPont);
  • Ethylene-methyl acrylate binary copolymer brand ELVALOY AC 1125 (DuPont);
  • Ethylene-butyl acrylate binary copolymer brand ELVALOY AC 34035 (DuPont);
  • G1 ECS13-4.5-534A (glass fiber diameter 13 ⁇ m, treated with coupling agent, Jushi Group);
  • G2 ECS10-4.5-T436H (glass fiber diameter 10 ⁇ m, treated with coupling agent, Taishan Glass Fiber Co., Ltd.);
  • G3 EMG200 (glass fiber diameter 13 ⁇ m, uncoupling agent treatment, Taishan Glass Fiber Co., Ltd.);
  • Example 6 Processing aids.
  • antioxidants hindered phenolic antioxidants 1010, phosphite antioxidants 168, organic sulfur antioxidants 412S, Lianlong
  • pigments zinc sulfide, Hens Mai; black mother PE2718, Cabot
  • lubricant polyolefin lubricant PED 521, Clariant; aliphatic carboxylate lubricant PETS, hair base
  • transesterification inhibitor sodium dihydrogen phosphate, Wuhan Hua Create
  • the weight ratio of the components in the processing aid is 2:1:1:10:10:5:5:3; the processing aids in other examples and comparative examples do not contain transesterification inhibitors, other All are the same as the processing aid in Example 6.
  • Examples 1-10 and Comparative Examples 1 to 4 are set in parts by weight.
  • the components, content selection and performance data of Specific Examples 1-10 and Comparative Examples 1 to 4 are shown in Table 1:
  • Comparative Example 1 only contains brominated flame retardants and antimony white
  • Comparative Example 2 only contains brominated flame retardants and nitrogen-containing smoke suppressants
  • Comparative Example 3 contains only Brominated flame retardant and flame retardant synergist; the ignition temperature of the high glow wire resistance of Comparative Examples 1 to 3 is significantly lower than that of Example 1.
  • Comparing Comparative Example 4 with Example 1 it can be seen that the alkali-free glass fiber in Example 1 has been treated with a coupling agent, and the alkali-free glass fiber in Comparative Example 4 has not been treated with a coupling agent; through the comparison of performance data, it can be seen that in Comparative Example 4 The ignition temperature of high glow wire resistance is lower than that of Example 1, and the tensile strength and Izod notched impact strength are also significantly worse than that of Example 1.
  • Example 10 Except that the bromine-based flame retardant is selected differently in Examples 7 and 8, the others are the same as Example 1. Through the comparison of performance data, it can be seen that the high glow wire ignition temperature in Examples 7 and 8 is lower than that in Example 1. , And the tensile strength and Izod notched impact strength are also slightly worse than Example 1. Except for the different selection of nitrogen-containing smoke suppressants in Example 9, the others are the same as Example 1. The comparison of performance data shows that the ignition temperature of the high-glow wire in Example 9 is lower than that in Example 1, and the drawing The strength and Izod notch impact strength are also slightly worse than those of Example 1. In Example 10, except the choice of phosphate synergist is different, the others are the same as in Example 1. From the comparison of performance data, it can be known that the high glow wire ignition temperature in Example 10 is lower than that in Example 1, and The tensile strength and Izod notched impact strength are also inferior to Example 1.
  • the nitrogen-containing brominated flame retardant, the nitrogen-containing smoke suppressant and the phosphorus-containing flame retardant synergist work together in an appropriate ratio to assist the alkali-free glass fiber treated with the coupling agent ,
  • a polyester composite material with high GWIT, high mechanical strength and meeting the strength requirements of electrical and electronic structural parts can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A polyester material having high glow-wire ignition temperature (GWIT) resistance, comprising the following components in parts by weight: 25-40 parts of a polyester resin, 25-40 parts of an alkali-free glass fiber, 18-30 parts of a brominated flame retardant, 3-8 parts of a nitrogen-containing smoke suppressant, and 2-10 parts of a phosphate flame retardant synergistic agent. The alkali-free glass fiber is an alkali-free glass fiber treated by a coupling agent. A halogen-containing flame retardant and a nitrogen-phosphorus compounding synergistic agent are effectively combined, and an antimony-containing compound is not contained, and thus, a glass fiber enhanced flame-retardant polyester material is obtained; and the polyester material has excellent mechanical properties, multiple colors, the wall thickness between 1.0-2.0 mm, and the GWIT reaching to 875°C or above. Moreover, further disclosed is a preparation method for the polyester material.

Description

一种具有耐高灼热丝起燃温度的聚酯材料及其制备方法Polyester material with high glow wire ignition temperature resistance and preparation method thereof 技术领域Technical field
本发明涉及高分子材料改性领域，尤其涉及一种具有耐高灼热丝起燃温度的聚酯材料及其制备方法。The invention relates to the field of polymer material modification, in particular to a polyester material with high glow wire resistance to ignition temperature and a preparation method thereof.
背景技术Background technique
聚对苯二甲酸丁二醇酯PBT和聚对苯二甲酸乙二醇酯PET是电子电气行业中作为功能结构件常用的两种热塑性聚酯材料，因结晶和线性饱和，其具有优良的电性能、机械强度和加工性，改性后的聚酯在电子电气、家电、汽车等领域得到广泛的应用。材料的安规要求也越来越严格，众多行业除了要求满足UL94的阻燃等级外，IEC60695标准中的灼热丝起燃温度(GWIT)要求也要强制执行，对于长期无人监管的电器所用塑料件标准提出GWIT必须满足≥775℃,而现在随着电子器械的功能实现越来越多，对特定部件如连接器、继电器外壳、断路器外壳等GWIT要求达到850℃或以上。Polybutylene terephthalate PBT and polyethylene terephthalate PET are two thermoplastic polyester materials commonly used as functional structural parts in the electronic and electrical industry. Due to crystallization and linear saturation, they have excellent electrical properties. Performance, mechanical strength and processability, the modified polyester has been widely used in the fields of electronics, electrical appliances, home appliances, and automobiles. The safety requirements of materials are becoming more and more stringent. In addition to meeting the UL94 flame retardant rating in many industries, the glow-wire ignition temperature (GWIT) requirements in the IEC60695 standard must also be enforced. For plastics used in electrical appliances that are unsupervised for a long time The component standard proposes that GWIT must meet ≥775°C, and now with the realization of more and more functions of electronic devices, GWIT requirements for specific components such as connectors, relay housings, circuit breaker housings, etc., must reach 850°C or above.
在实际的GWIT测试过程中，阻燃玻纤增强的聚酯材料在较薄厚度级别(如0.75mm或以下)和较高厚度级别(如3.0mm或以上)均可以获得较高的GWIT，但在中间厚度如1.0～2.0mm的GWIT较低，如：同一款阻燃材料在1.5mm厚度GWIT为700℃或725℃，但在3.0mm或0.75mm厚度GWIT可以达到750℃或775℃。In the actual GWIT test process, the flame-retardant glass fiber reinforced polyester material can obtain a higher GWIT at a thinner thickness level (such as 0.75mm or less) and a higher thickness level (such as 3.0mm or above), but In the middle thickness, such as 1.0～2.0mm, the GWIT is lower. For example, the same flame retardant material can reach 700°C or 725°C at a thickness of 1.5mm, but can reach 750°C or 775°C at a thickness of 3.0mm or 0.75mm.
现有技术中，高灼热丝起燃温度的有卤阻燃聚酯材料中大多数都使用了锑化合物协效，而锑化合物尤其是锑白被世界卫生组织国际癌症研究机构在2017年列为2B类致癌物清单中，直接接触时皮肤可能会有过敏反应，产生炎症，影响生产；且这些材料的GWIT很少见报道厚度在1.0-2.0mm为850℃以上，即使有做到2.0mm为875℃，但力学性能较低，强度也很难满足电子电气行业中塑胶制品的作为连接或支撑作用功能性测试要求。In the prior art, most halogenated flame-retardant polyester materials with high glow wire ignition temperature use antimony compounds as synergistic effects, and antimony compounds, especially antimony white, were listed by the International Agency for Research on Cancer of the World Health Organization in 2017. In the list of 2B carcinogens, the skin may have allergic reactions, inflammation, and affect production when directly contacted; and GWIT of these materials is rarely reported to be 1.0-2.0mm above 850℃, even if it is 2.0mm 875°C, but the mechanical properties are low, and the strength is difficult to meet the functional test requirements of plastic products as a connection or support in the electronic and electrical industry.
发明内容Summary of the invention
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具有耐高灼热丝起燃温度的聚酯材料。本发明采用有卤阻燃剂与氮磷复配协效剂有效地结合，不含锑化合物，获得玻纤增强阻燃的聚酯材料，该聚酯材料具有优异的力学性能、多种颜色和壁厚在1.0-2.0mm之间GWIT达到875℃或以上。Based on this, the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a polyester material with high glow-wire resistance. The present invention uses halogenated flame retardant and nitrogen-phosphorus compound synergist to effectively combine without antimony compound to obtain glass fiber reinforced flame-retardant polyester material. The polyester material has excellent mechanical properties, a variety of colors and The wall thickness is between 1.0-2.0mm and the GWIT reaches 875°C or above.
为实现上述目的，本发明所采取的技术方案为：一种具有耐高灼热丝起燃温度的聚酯材料，包括如下重量份的成分：聚酯树脂25～40份、无碱玻璃纤维25～40份、溴系阻燃剂18～30份、含氮抑烟剂3～8份和磷酸酯类阻燃协效剂2～10份；所述无碱玻璃纤维为经过偶联剂处理过的无碱玻璃纤维。In order to achieve the above-mentioned object, the technical solution adopted by the present invention is: a polyester material with high glow wire ignition temperature resistance, including the following components by weight: 25-40 parts of polyester resin, 25- 40 parts of alkali-free glass fiber 40 parts, 18-30 parts of brominated flame retardant, 3-8 parts of nitrogen-containing smoke suppressant and 2-10 parts of phosphate flame retardant synergist; the alkali-free glass fiber is treated with coupling agent Alkali-free glass fiber.
本申请溴系阻燃剂、含氮抑烟剂和含磷阻燃协效剂三者在上述含量范围内，能够发挥较好的协同增效作用，使该聚酯材料具有较好的阻燃效果、机械强度高、具有耐高灼热丝起燃温度。The brominated flame retardant, the nitrogen-containing smoke suppressant and the phosphorus-containing flame retardant synergist of the present application can play a better synergistic effect within the above-mentioned content range, so that the polyester material has better flame retardancy Effect, high mechanical strength, high resistance to high glow wire ignition temperature.
玻璃纤维的原丝在拉丝过程中经含硅烷偶联剂的浸润剂涂覆，然后烘干、切粒得到偶联剂处理的无碱玻纤；偶联剂处理后的玻纤与聚酯树脂界面结合紧密，对复合材料的机械强度的提升大有帮助。The raw fiber of glass fiber is coated with a sizing agent containing silane coupling agent during the drawing process, then dried and pelletized to obtain alkali-free glass fiber treated with coupling agent; glass fiber and polyester resin treated with coupling agent The interface is tightly bonded, which greatly contributes to the improvement of the mechanical strength of the composite material.
优选地，所述无碱玻璃纤维的直径为10～13μm。Preferably, the diameter of the alkali-free glass fiber is 10-13 μm.
优选地，所述聚酯树脂为聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯中的至少一种。Preferably, the polyester resin is at least one of polybutylene terephthalate and polyethylene terephthalate.
优选地，所述溴系阻燃剂为溴代三嗪。溴代三嗪的溴含量比普通的其它溴类阻燃剂溴含量高，且含有氮，其阻燃机理为去吸热分解型，阻燃效率更高。Preferably, the brominated flame retardant is brominated triazine. Bromotriazine has a higher bromine content than other ordinary bromine flame retardants and contains nitrogen. Its flame retardant mechanism is de-endothermic decomposition type, and its flame retardant efficiency is higher.
优选地，所述含氮抑烟剂为三聚氰胺氰尿酸盐、三聚氰胺聚磷酸盐中的至少一种。三聚氰胺类含氮抑烟剂与磷系阻燃剂有很好的协调阻燃效果，可以做到用量少，阻燃效果好且发烟量少等特点。Preferably, the nitrogen-containing smoke suppressant is at least one of melamine cyanurate and melamine polyphosphate. The melamine-based nitrogen-containing smoke suppressant and the phosphorus-based flame retardant have a good coordination flame retardant effect, which can achieve the characteristics of low dosage, good flame retardant effect and low smoke emission.
优选地，所述磷酸酯类阻燃协效剂为磷酸双苯基酯。Preferably, the phosphate flame retardant synergist is bisphenyl phosphate.
优选地，所述的具有耐高灼热丝起燃温度的聚酯材料，还包含如下重量份的成分：增韧剂0～8份和加工助剂0～5份。Preferably, the polyester material with high glow-wire resistance to ignition temperature further contains the following components in parts by weight: 0-8 parts of toughening agent and 0-5 parts of processing aid.
更优选地，所述增韧剂为乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物、乙烯-丙烯酸甲酯二元共聚物、乙烯-丙烯酸丁酯二元共聚物中的至少一种；所述加工助剂包含复合抗氧体系、润滑剂和颜料，所述复合抗氧体系由受阻酚类抗氧剂、亚磷酸酯抗氧剂、有机硫抗氧剂复配组成，所述润滑剂为脂肪族羧酸酯润滑剂、聚烯烃类润滑剂中的至少一种。More preferably, the toughening agent is at least one of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate binary copolymer, and ethylene-butyl acrylate binary copolymer The processing aid includes a composite antioxidant system, a lubricant and a pigment, the composite antioxidant system is composed of hindered phenolic antioxidants, phosphite antioxidants, and organic sulfur antioxidants, the lubricating The agent is at least one of an aliphatic carboxylate lubricant and a polyolefin lubricant.
同时，本发明还提供一种所述具有耐高灼热丝起燃温度的聚酯材料的制备方法，所述方法为：At the same time, the present invention also provides a method for preparing the polyester material with high glow wire resistance to ignition temperature, and the method is:
先将聚酯树脂在120～140℃下预干燥4～6小时，然后将干燥后的聚酯树脂与除无碱玻璃纤维之外的其他成分一起进行混合，混合均匀后，将混合物料送入双螺杆挤出机中，同时在双螺杆挤出机侧喂口加入无碱玻璃纤维，经挤出、拉条、冷却、切粒、干燥、包装，得到具有耐高灼热丝起燃温度的聚酯材料。First, pre-dry the polyester resin at 120-140°C for 4-6 hours, then mix the dried polyester resin with other ingredients except for the alkali-free glass fiber, and then send the mixture into In the twin-screw extruder, the alkali-free glass fiber is added to the side feeding port of the twin-screw extruder at the same time. After extrusion, drawing, cooling, pelletizing, drying, and packaging, a polymer with high glow wire ignition temperature resistance is obtained. Ester material.
优选地，所述双螺杆挤出机的喂料为450～800kg/小时；所述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220-230℃、230-240℃、230-240℃、240-250℃、250-260℃、240-250℃、240-250℃、230-240℃、230-240℃，所述双螺杆挤出机的螺杆转速为250～400rpm。Preferably, the feed of the twin-screw extruder is 450-800kg/hour; the temperature of each section of the twin-screw extruder from the feeding port to the die is 220-230°C, 230-240 ℃, 230-240℃, 240-250℃, 250-260℃, 240-250℃, 240-250℃, 230-240℃, 230-240℃, the screw speed of the twin screw extruder is 250～ 400rpm.
相对于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明得到的具有耐高灼热丝起燃温度的无锑溴系阻燃增强聚酯复合材料，在阻燃性具有UL-94标准V-0等级的同时，在1.0-2.0mm之间厚度上的GWIT能达到875℃或以上；(1) The antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow-wire ignition temperature resistance obtained by the present invention has UL-94 standard V-0 level of flame retardancy, and is within 1.0-2.0mm The GWIT in the thickness can reach 875℃ or above;
(2)本发明得到的具有耐高灼热丝起燃温度的无锑溴系阻燃增强聚酯复合材料，拉伸强度在100MPa以上，缺口冲击强度在7.5kJ/m 2以上(ISO标准)； (2) The antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow wire ignition temperature resistance obtained by the present invention has a tensile strength of more than 100MPa and a notched impact strength of more than 7.5kJ/m 2 (ISO standard);
(3)本发明得到的具有耐高灼热丝起燃温度的无锑溴系阻燃增强聚酯复合材料，不含锑及其化合物，在环境物质管控方面避免了因锑化合物可能带来重金属超标等问题以及使用锑化合物可能导致的职业病等风险。(3) The antimony-free bromine-based flame-retardant reinforced polyester composite material with high glow wire ignition temperature resistance obtained in the present invention does not contain antimony and its compounds, and avoids the possibility of heavy metals exceeding the standard caused by antimony compounds in the management and control of environmental substances Problems such as the use of antimony compounds may cause occupational diseases and other risks.
具体实施方式detailed description
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。In order to better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.
本申请实施例及对比例中聚酯材料的制备方法如下：The preparation methods of the polyester materials in the examples and comparative examples of this application are as follows:
(1)将聚酯树脂在130℃下干燥4～6小时，水分控制在小于0.03％；(1) Dry the polyester resin at 130°C for 4-6 hours, and control the moisture content to less than 0.03%;
(2)按照配比准备好各种原料；(2) Prepare various raw materials according to the ratio;
(3)将经干燥处理后的聚酯树脂与除无碱玻璃纤维之外的其他成分按比例进行高速搅拌混料机混合均匀或单独通过计量喂料器进入预混机得到预混物；(3) Mix the dried polyester resin and other ingredients except for alkali-free glass fiber in a high-speed mixing mixer in proportion, or enter the premixer through a metering feeder to obtain a premix;
(4)将上述混合物料送入双螺杆挤出机中，调节喂料量为450～800kg/小时，在双螺杆挤出机中侧喂口加入无碱玻璃纤维，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230℃、240℃、240℃、250℃、260℃、250℃、240℃、230℃、230℃，螺杆转速为400rpm，在双螺杆挤出机的输送和剪切作用下，充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥，最后包装。(4) Feed the above mixture into a twin-screw extruder, adjust the feed rate to 450-800kg/hour, add alkali-free glass fiber to the side feeding port of the twin-screw extruder, and each of the twin-screw extruder The temperature of the segment screw from the feeding port to the die head is 230℃, 240℃, 240℃, 250℃, 260℃, 250℃, 240℃, 230℃, 230℃, the screw speed is 400rpm, in twin screw extrusion Under the conveying and shearing action of the machine, it is fully melted and plasticized, kneaded and mixed, extruded through the machine head, stretched, cooled, pelletized, dried, and finally packaged.
具体所得产品的性能测试方法如下：The specific performance test methods of the obtained products are as follows:
(1)将挤出切粒得到的产品在120-130℃下烘干，时间3-4小时；(1) Dry the product obtained by extrusion and pelletizing at 120-130°C for 3-4 hours;
(2)按照相应的标准注塑制备测试样片；(2) Prepare test specimens by injection molding according to corresponding standards;
(3)拉伸强度按照ISO 527标准测试，悬臂梁缺口冲击强度按照ISO 180标准测试，阻燃性能按照UL 94标准测试，GWIT按照IEC 60695标准测试。(3) Tensile strength is tested according to ISO 527 standard, Izod notched impact strength is tested according to ISO 180 standard, flame retardant performance is tested according to UL 94 standard, and GWIT is tested according to IEC 60695 standard.
实施例和对比例中用到的主要代表材料如下：The main representative materials used in the examples and comparative examples are as follows:
A聚酯树脂A polyester resin
A1：PBT树脂，台湾长春1100-211M；A1: PBT resin, Changchun 1100-211M, Taiwan;
A2：PET树脂，仪征化纤FG600；A2: PET resin, Yizheng Chemical Fiber FG600;
B溴系阻燃剂B bromine flame retardant
B1：溴化环氧F-2100，以色列ICL；B1: Brominated epoxy F-2100, Israel ICL;
B2：溴代三嗪FR-245，以色列ICL；B2: Bromotriazine FR-245, Israel ICL;
B3：十溴二苯乙烷8010，雅宝；B3: Decabromodiphenylethane 8010, Albemarle;
C锑白：选用S-05N，辰州锑业；C antimony white: choose S-05N, Chenzhou antimony industry;
D含氮抑烟剂D Nitrogen-containing smoke suppressant
D1：MCA(三聚氰胺氰尿酸盐)，四川精细化工；D1: MCA (Melamine Cyanurate), Sichuan Fine Chemical Industry;
D2：MPP(三聚氰胺聚磷酸盐)，寿光卫东化工；D2: MPP (Melamine Polyphosphate), Shouguang Weidong Chemical Industry;
D3：APP(多聚磷酸铵)，捷尔思化工；D3: APP (ammonium polyphosphate), Jieersi Chemical;
E磷酸酯类协效剂：E phosphate synergist:
E1：磷酸双苯基酯；WSFR-PX220(对苯二酚双(二苯基磷酸酯))，万盛；E1: Bisphenyl phosphate; WSFR-PX220 (hydroquinone bis(diphenyl phosphate)), Wansheng;
E2：磷酸苯基酯；WSFR-RDP(间苯二酚(二苯基磷酸酯))，万盛；E2: Phenyl phosphate; WSFR-RDP (resorcinol (diphenyl phosphate)), Wansheng;
F增韧剂F toughening agent
F1：乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物，牌号PTW(杜邦)；F1: Ethylene-acrylate-glycidyl methacrylate terpolymer, grade PTW (DuPont);
F2：乙烯-丙烯酸甲酯二元共聚物，牌号ELVALOY AC 1125(杜邦)；F2: Ethylene-methyl acrylate binary copolymer, brand ELVALOY AC 1125 (DuPont);
F3：乙烯-丙烯酸丁酯二元共聚物，牌号ELVALOY AC 34035(杜邦)；F3: Ethylene-butyl acrylate binary copolymer, brand ELVALOY AC 34035 (DuPont);
G无碱玻璃纤维G alkali-free glass fiber
G1：ECS13-4.5-534A(玻纤直径13μm，偶联剂处理，巨石集团)；G1: ECS13-4.5-534A (glass fiber diameter 13μm, treated with coupling agent, Jushi Group);
G2：ECS10-4.5-T436H(玻纤直径10μm，偶联剂处理，泰山玻璃纤维有限公司)；G2: ECS10-4.5-T436H (glass fiber diameter 10μm, treated with coupling agent, Taishan Glass Fiber Co., Ltd.);
G3：EMG200(玻纤直径13μm，未偶联剂处理，泰山玻璃纤维有限公司)；G3: EMG200 (glass fiber diameter 13μm, uncoupling agent treatment, Taishan Glass Fiber Co., Ltd.);
H：加工助剂，实施例6中分别选用抗氧剂(受阻酚类抗氧剂1010，亚磷酸酯抗氧剂168，有机硫抗氧剂412S，利安隆)，颜料(硫化锌，亨斯迈；黑色母PE2718，卡博特)，润滑剂(聚烯烃类润滑剂PED 521，科莱恩；脂肪族羧酸酯润滑剂PETS，发基)，酯交换抑制剂(磷酸二氢钠，武汉华创)，加工助剂中各成分的重量比为2:1:1:10:10:5:5:3；其他实施例及对比例中的加工助剂除不含有酯交换抑制剂外，其他均与实施例6中的加工助剂相同。H: Processing aids. In Example 6, antioxidants (hindered phenolic antioxidants 1010, phosphite antioxidants 168, organic sulfur antioxidants 412S, Lianlong), pigments (zinc sulfide, Hens Mai; black mother PE2718, Cabot), lubricant (polyolefin lubricant PED 521, Clariant; aliphatic carboxylate lubricant PETS, hair base), transesterification inhibitor (sodium dihydrogen phosphate, Wuhan Hua Create), the weight ratio of the components in the processing aid is 2:1:1:10:10:5:5:3; the processing aids in other examples and comparative examples do not contain transesterification inhibitors, other All are the same as the processing aid in Example 6.
本申请设置实施例1～10及对比例1～4，以重量份计，具体实施例1～10及对比例1～4的成分、含量选择及性能数据如表1所示：In this application, Examples 1-10 and Comparative Examples 1 to 4 are set in parts by weight. The components, content selection and performance data of Specific Examples 1-10 and Comparative Examples 1 to 4 are shown in Table 1:
表1 实施例1～10及对比例1～4的成分、含量选择及性能数据Table 1 Composition, content selection and performance data of Examples 1-10 and Comparative Examples 1-4
Figure PCTCN2020136319-appb-000001
Figure PCTCN2020136319-appb-000001
Figure PCTCN2020136319-appb-000002
Figure PCTCN2020136319-appb-000002
根据表2可以看出，与实施例1相比，对比例1只含有溴系阻燃剂和锑白，对比例2只含有溴系阻燃剂和含氮抑烟剂，对比例3只含有溴系阻燃剂和阻燃协效剂；对比例1～3的耐高灼热丝起燃温度显著低于实施例1。将对比例4与实 施例1对比可知，实施例1中无碱玻璃纤维经过偶联剂处理，对比例4中无碱玻璃纤维没有经过偶联剂处理；通过性能数据对比可知，对比例4中的耐高灼热丝起燃温度低于实施例1，且拉伸强度、悬臂梁缺口冲击强度也显著差于实施例1。It can be seen from Table 2 that compared with Example 1, Comparative Example 1 only contains brominated flame retardants and antimony white, Comparative Example 2 only contains brominated flame retardants and nitrogen-containing smoke suppressants, and Comparative Example 3 contains only Brominated flame retardant and flame retardant synergist; the ignition temperature of the high glow wire resistance of Comparative Examples 1 to 3 is significantly lower than that of Example 1. Comparing Comparative Example 4 with Example 1, it can be seen that the alkali-free glass fiber in Example 1 has been treated with a coupling agent, and the alkali-free glass fiber in Comparative Example 4 has not been treated with a coupling agent; through the comparison of performance data, it can be seen that in Comparative Example 4 The ignition temperature of high glow wire resistance is lower than that of Example 1, and the tensile strength and Izod notched impact strength are also significantly worse than that of Example 1.
实施例7、8中除溴系阻燃剂选择不同外，其他均与实施例1相同；通过性能数据对比可知，实施例7、8中的耐高灼热丝起燃温度、低于实施例1，且拉伸强度、悬臂梁缺口冲击强度也略差于实施例1。实施例9中除含氮抑烟剂的选择不同外，其他均与实施例1相同；通过性能数据对比可知，实施例9中的耐高灼热丝起燃温度低于实施例1，且拉伸强度、悬臂梁缺口冲击强度也略差于实施例1。实施例10中除磷酸酯类协效剂的选择不同外，其他均与实施例1相同；通过性能数据对比可知，实施例10中的耐高灼热丝起燃温度低于实施例1，且拉伸强度、悬臂梁缺口冲击强度也差于实施例1。Except that the bromine-based flame retardant is selected differently in Examples 7 and 8, the others are the same as Example 1. Through the comparison of performance data, it can be seen that the high glow wire ignition temperature in Examples 7 and 8 is lower than that in Example 1. , And the tensile strength and Izod notched impact strength are also slightly worse than Example 1. Except for the different selection of nitrogen-containing smoke suppressants in Example 9, the others are the same as Example 1. The comparison of performance data shows that the ignition temperature of the high-glow wire in Example 9 is lower than that in Example 1, and the drawing The strength and Izod notch impact strength are also slightly worse than those of Example 1. In Example 10, except the choice of phosphate synergist is different, the others are the same as in Example 1. From the comparison of performance data, it can be known that the high glow wire ignition temperature in Example 10 is lower than that in Example 1, and The tensile strength and Izod notched impact strength are also inferior to Example 1.
综上，从以上数据看出，含氮的溴系阻燃剂与含氮抑烟剂以及含磷阻燃协效剂通过合适比例的共同作用，辅助于偶联剂处理过的无碱玻纤，可以获得GWIT高、力学强度高、符合电子电气结构件强度要求的聚酯复合材料。In summary, it can be seen from the above data that the nitrogen-containing brominated flame retardant, the nitrogen-containing smoke suppressant and the phosphorus-containing flame retardant synergist work together in an appropriate ratio to assist the alkali-free glass fiber treated with the coupling agent , A polyester composite material with high GWIT, high mechanical strength and meeting the strength requirements of electrical and electronic structural parts can be obtained.
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。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to 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 (9)

  1. 一种具有耐高灼热丝起燃温度的聚酯材料，其特征在于，包括如下重量份的成分：聚酯树脂25～40份、无碱玻璃纤维25～40份、溴系阻燃剂18～30份、含氮抑烟剂3～8份和磷酸酯类阻燃协效剂2～10份；所述无碱玻璃纤维为经过偶联剂处理过的无碱玻璃纤维。A polyester material with high glow-wire ignition temperature resistance, which is characterized in that it comprises the following components by weight: 25-40 parts of polyester resin, 25-40 parts of alkali-free glass fiber, and 18-40 parts of brominated flame retardant. 30 parts, 3-8 parts of nitrogen-containing smoke suppressant and 2-10 parts of phosphate flame retardant synergist; the alkali-free glass fiber is alkali-free glass fiber that has been treated with a coupling agent.
  2. 如权利要求1所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，所述聚酯树脂为聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯中的至少一种。The polyester material with high glow wire ignition temperature resistance according to claim 1, wherein the polyester resin is polybutylene terephthalate, polyethylene terephthalate At least one of.
  3. 如权利要求1所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，所述溴系阻燃剂为溴代三嗪。The polyester material with high glow-wire resistance to ignition temperature according to claim 1, wherein the brominated flame retardant is brominated triazine.
  4. 如权利要求1所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，所述含氮抑烟剂为三聚氰胺氰尿酸盐、三聚氰胺聚磷酸盐中的至少一种。The polyester material with high glow-wire resistance to ignition temperature according to claim 1, wherein the nitrogen-containing smoke suppressant is at least one of melamine cyanurate and melamine polyphosphate.
  5. 如权利要求1所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，所述磷酸酯类阻燃协效剂为磷酸双苯基酯。The polyester material with high glow-wire resistance to ignition temperature according to claim 1, wherein the phosphate flame retardant synergist is bisphenyl phosphate.
  6. 如权利要求1～5任一项所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，还包含如下重量份的成分：增韧剂0～8份和加工助剂0～5份。The polyester material with high glow wire ignition temperature resistance according to any one of claims 1 to 5, characterized in that it further comprises the following components by weight: 0-8 parts of toughening agent and 0- 8 parts of processing aid. 5 servings.
  7. 如权利要求6所述的具有耐高灼热丝起燃温度的聚酯材料，其特征在于，所述增韧剂为乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物、乙烯-丙烯酸甲酯二元共聚物、乙烯-丙烯酸丁酯二元共聚物中的至少一种；所述加工助剂包含复合抗氧体系、润滑剂和颜料，所述复合抗氧体系由受阻酚类抗氧剂、亚磷酸酯抗氧剂、有机硫抗氧剂复配组成，所述润滑剂为脂肪族羧酸酯润滑剂、聚烯烃类润滑剂中的至少一种。The polyester material with high glow-wire resistance to ignition temperature of claim 6, wherein the toughening agent is ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-acrylic acid methyl ester At least one of ester binary copolymer and ethylene-butyl acrylate binary copolymer; the processing aid includes a composite antioxidant system, a lubricant and a pigment, and the composite antioxidant system is composed of a hindered phenolic antioxidant , Phosphite antioxidant, organic sulfur antioxidant compound composition, the lubricant is at least one of aliphatic carboxylate lubricant and polyolefin lubricant.
  8. 一种如权利要求1～7任一项所述具有耐高灼热丝起燃温度的聚酯材料的制备方法，其特征在于，所述方法为：A method for preparing a polyester material with high glow wire resistance to ignition temperature according to any one of claims 1 to 7, characterized in that the method is:
    先将聚酯树脂在120～140℃下预干燥4～6小时，然后将干燥后的聚酯树脂与除无碱玻璃纤维之外的其他成分一起进行混合，混合均匀后，将混合物料送入双螺杆挤出机中，同时在双螺杆挤出机侧喂口加入无碱玻璃纤维，经挤出、拉 条、冷却、切粒、干燥、包装，得到具有耐高灼热丝起燃温度的聚酯材料。First, pre-dry the polyester resin at 120-140°C for 4-6 hours, then mix the dried polyester resin with other ingredients except for the alkali-free glass fiber, and then send the mixture into In the twin-screw extruder, the alkali-free glass fiber is added to the side feeding port of the twin-screw extruder at the same time. After extrusion, drawing, cooling, pelletizing, drying, and packaging, a polymer with high glow wire ignition temperature resistance is obtained. Ester material.
  9. 如权利要求8所述具有耐高灼热丝起燃温度的聚酯材料的制备方法，其特征在于，所述双螺杆挤出机的喂料为450～800kg/小时；所述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220-230℃、230-240℃、230-240℃、240-250℃、250-260℃、240-250℃、240-250℃、230-240℃、230-240℃，所述双螺杆挤出机的螺杆转速为250～400rpm。The method for preparing a polyester material with high glow wire resistance to ignition temperature according to claim 8, wherein the feed of the twin-screw extruder is 450-800 kg/hour; the twin-screw extruder The temperature of each section of the screw from the feeding port to the nose is 220-230℃, 230-240℃, 230-240℃, 240-250℃, 250-260℃, 240-250℃, 240-250℃, 230-240°C, 230-240°C, and the screw speed of the twin-screw extruder is 250-400 rpm.
PCT/CN2020/136319 2020-06-23 2020-12-15 Polyester material having high glow-wire ignition temperature resistance and preparation method therefor WO2021258674A1 (en)

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