WO2021120863A1 - Polyamide composition and preparation method therefor - Google Patents

Polyamide composition and preparation method therefor Download PDF

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Publication number
WO2021120863A1
WO2021120863A1 PCT/CN2020/124012 CN2020124012W WO2021120863A1 WO 2021120863 A1 WO2021120863 A1 WO 2021120863A1 CN 2020124012 W CN2020124012 W CN 2020124012W WO 2021120863 A1 WO2021120863 A1 WO 2021120863A1
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soap salt
metal soap
butyl
polyamide composition
tert
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PCT/CN2020/124012
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French (fr)
Chinese (zh)
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郑一泉
叶南飚
何勇
丁超
冯德才
金雪峰
戴剑
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金发科技股份有限公司
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Publication of WO2021120863A1 publication Critical patent/WO2021120863A1/en

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08L2205/24—Crystallisation aids

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polyamide composition and a preparation method thereof.
  • Polyamide resin has excellent mechanical properties, excellent barrier properties, heat resistance, abrasion resistance, chemical corrosion resistance and other excellent comprehensive properties, and is widely used in machinery manufacturing, power tools, electronic appliances, and transportation.
  • polyamide resins are more likely to be carbonized at high temperatures because they contain more small molecular compounds.
  • the polyamide melt has a strong adhesion effect to the metal, it is impossible to completely remove it every time the machine is shut down, so that the produced product always has a thin layer of plastic melt.
  • the body firmly adheres to the die of the extruder.
  • the melt performance of the die accessory produced will be significantly thermally degraded, and finally it will gradually turn yellow and zoom. Eventually become carbides.
  • the mainstream method is to periodically remove the carbide from the die through equipment modification, or to clean the die after the injection is completed, but it does not reduce the carbide from the root cause, and there is still carburization of the die. The risk of objects falling into normal products.
  • Chinese patent CN103707483A discloses a device for preventing the generation of carbides at the position of the die during the granulation process.
  • the device includes a die plate and an air inlet pipe.
  • the die plate has a die hole, and the outlet of the air inlet pipe is located in the inner die of the air collecting hood. The position above the hole.
  • This technology is used in the process flow of polyamide or modified polyamide granulation, which can prevent the polyamide melt or modified polyamide melt from sticking around the die, and it will be exposed to the high temperature of the die and oxygen in the air for a long time. Under the action of, the polyamide melt adhered around the die of the discharge bar is oxidized and turned yellow or even black.
  • the present invention found that antioxidants that can decompose peroxides have better anti-oxidation effects at lower temperatures (100-150°C) for a long time, but for short-term higher temperatures (260°C and above, such as polyamides). In some cases, the processing temperature will exceed 330°C or even higher). The oxidation resistance is almost zero. Even if the added amount is increased, the effect of reducing the carbides in the die cannot be achieved. Larger molecular benzofuranone compounds can capture carbon free radicals, and can also have an excellent antioxidant effect at temperatures above 260°C.
  • Benzofuranone compounds are a kind of stabilizer and antioxidant, and some compounds are used as antioxidants for fats, oils and foods. See Chinese patent application 20038001064960, but this patent only uses its long-term stability.
  • Chinese patent application 2005101380935 discloses a stabilizing composition in which benzofuranone is used as a stabilizer, and its use as an antioxidant is not disclosed.
  • Chinese patent application 2012100225970 discloses the application of a small molecule benzofuranone compound as an antioxidant in polypropylene. It also discloses that the benzofuranone compound can capture carbon free radicals to reach the end of the chain segment and play a role in resisting oxidation.
  • this patent uses a small molecule benzofuranone compound, which has a too small molecular weight and insufficient heat resistance (it loses its oxidation resistance above 260°C). Although it can capture C free radicals, it can only be processed at a relatively low temperature of polypropylene materials (generally less than 200°C and not more than 230°C), thus losing the function of inhibiting the formation of carbides in the die.
  • the anti-oxidation performance of this compound is similar to that of other kinds of compounds (such as antioxidants 10989 and 168), and the performance of inhibiting die carbides above 260°C is even inferior to the above two kinds of anti-oxidation.
  • the purpose of the present invention is to provide a polyamide composition that can improve the carbonization of the die during injection molding or pelletizing.
  • a polyamide composition in parts by weight, comprising the following components:
  • n 0, 1, 2 or 3;
  • R 1 and R 2 are each independently hydrogen or C1-C8 alkyl,
  • R 3 and R 4 are each independently hydrogen or C1-C6 alkyl, but not at the same time C1-C6 alkyl;
  • R 5 and R 6 are each independently hydrogen or C1-C6 alkyl, but are not C1-C6 alkyl at the same time;
  • R 7 is hydrogen or hydroxyl.
  • the polyamide resin is selected from at least one of aliphatic polyamides, semi-aromatic polyamides, and polylactams.
  • the polyamide is selected from polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine or cyclic diamine, such as PA6, PA66, PA610, PA612, PA1212, PA56, PA46, MXD6 , PA510; or polyamide obtained by polycondensation of at least one aromatic dicarboxylic acid and at least one aliphatic diamine, such as polyterephthalamide, according to isophthalamide, polyaramid, specifically PA9T, PA10T; or polyamide obtained by polycondensation of at least one amino acid or lactam with itself, such as PA6, PA7, PA11, PA12; or a mixture or copolymer of the above polyamides.
  • polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine or cyclic diamine such as PA6, PA66, PA610, PA612, PA1212, PA56, PA46,
  • the benzofuranone compound is preferably [4-tert-butyl-2-(5-tert-butyl-2-onyl-3hydro-benzofuran-3-yl)phenyl] -3,5-Di(tert-butyl)-4-hydroxy-benzoic acid ester.
  • the said K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt of which Zn metal soap salt and Al metal soap salt are preferred.
  • montanic acid generally has a carbon atom of 28- 34 acid.
  • the number of carbon atoms of stearic acid is generally about 18.
  • glass fiber can be added. In parts by weight, it also includes 0-50 parts of glass fiber; the glass fiber is selected from at least one of E glass, H glass, R, S glass, D glass, C glass, and quartz glass.
  • the present invention has the following beneficial effects
  • the present invention uses benzofuranone compounds to completely It can withstand the high temperature of melting, and its ability to capture carbon radicals cooperates with the nucleation of the soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al, which can improve the degree of carbonization of the die.
  • the raw materials used in the present invention are derived from commercially available products.
  • PA6 HY2800A, Haiyang Chemical Fiber Group
  • PA-MXD6 RENY 1002H, Mitsubishi Chemical Corporation;
  • Benzofuranone compounds I [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]benzoate;
  • Benzofuranone compound N 3,4-dibutyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one;
  • Hindered phenolic antioxidant Irganox 1098, BASF China Co., Ltd.;
  • Fatty acid ester 1 LOXIOL G 32, EmeryOleochemicals LLC;
  • Table 1 The distribution ratios (parts by weight) and test results of the polyamide compositions of Examples 1-4
  • Example 1 Example 2
  • Example 3 Example 4
  • PA6 80 To To To PA66 To 80 To To PA10T To To 80 To MXD6 To To To 80
  • Benzofuranone compounds I 0.2 0.05 0.4 1.2
  • Calcium montanate 0.5 0.8 1.0 1.5 Carbide appearance time in the die, min 300 330 350 380
  • PA6 PA66, PA10T, and MXD6, PA6 is the easiest to form die carbide.
  • Table 2 Distribution ratios (parts by weight) and test results of each group of the compositions of Examples 5-8
  • Example 10 PA6 80 80 80 80 80 80 80 80 Benzofuranone compounds I 0.2 0.2 0.2 0.2 0.2 To To Benzofuranone compounds II To To To To 0.2 To Benzofuranone compounds III To To To To To 0.2 Sodium montanate 0.5 To To To 0.5 0.5 Zinc montanate To 0.5 To To To To Aluminum montanate To To 0.5 To To To Calcium stearate To To To To 0.5 To To To To Carbide appearance time in the die, min 360 450 500 230 600 430

Abstract

Provided is a polyamide composition, which may effectively improve the formation of a carbide at a die orifice during injection molding or granulation. The present invention improves the formation of a carbide at a die orifice during injection molding by means of the synergistic effect of a benzofuranone compound and a soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al metals. Specifically, a benzofuranone compound has the function of capturing a C free radical in polyamide, and the soap salt of the K/Na/Ca/Mg/Ba/Zn/Li/Al metals may have a nucleation effect, together preventing the local temperature during injection molding from being too high thereby leading to the formation of a carbide, and especially preventing the adhesion thereof to a die orifice.

Description

一种聚酰胺组合物及其制备方法Polyamide composition and preparation method thereof 技术领域Technical field
本发明涉及高分子材料技术领域，特别是涉及一种聚酰胺组合物及其制备方法。The invention relates to the technical field of polymer materials, in particular to a polyamide composition and a preparation method thereof.
背景技术Background technique
聚酰胺树脂具有优良的机械性能、优良的阻隔性能、耐热性、耐磨性、耐化学腐蚀等优异的综合性能，广泛应用于机械制造业、电动工具、电子电器及交通运输等领域。Polyamide resin has excellent mechanical properties, excellent barrier properties, heat resistance, abrasion resistance, chemical corrosion resistance and other excellent comprehensive properties, and is widely used in machinery manufacturing, power tools, electronic appliances, and transportation.
一般的，相比于聚丙烯、聚乙烯等热塑性树脂，聚酰胺中因为其含有更多的小分子化合物，因此聚酰胺树脂更容易高温碳化。具体的，由于聚酰胺熔体对于金属来说具有着较强的粘附作用，因此在每次停机时都不可能会完全排除干净，从而使得生产出的产品总会有一层薄薄的塑料熔体牢牢的粘附在挤出机的口模附近，当设备处于连续高温情况下，因此就会使生产出的口模附件的熔体性能发生明显的热劣化，最后逐步变黄、变焦，最终成为碳化物。按照常规的停机方式，机头的模口以及进料口的两端都没有采取任何的有效措施，从而导致空气进入到机内而发生氧化，最终促使机内所残留的塑料热劣化更加的严重，给超高分子聚乙烯衬板的碳化提供了非常有利的条件。由于设备所采用的嗾使金属结构，也就使得其与塑料的热膨胀率具有较大的差别，已经碳化的塑料对于金属来说具有着较低的附着性，因此很容易从设备的机筒内壁、机头内壁以及螺杆上脱落下来，最终混入到塑料熔体中，使得生产出的超高分子聚乙烯衬板出现内外壁黑点较多，容易出现穿洞或者是渗漏等诸多质量问题。Generally, compared to thermoplastic resins such as polypropylene and polyethylene, polyamide resins are more likely to be carbonized at high temperatures because they contain more small molecular compounds. Specifically, because the polyamide melt has a strong adhesion effect to the metal, it is impossible to completely remove it every time the machine is shut down, so that the produced product always has a thin layer of plastic melt. The body firmly adheres to the die of the extruder. When the equipment is under continuous high temperature, the melt performance of the die accessory produced will be significantly thermally degraded, and finally it will gradually turn yellow and zoom. Eventually become carbides. According to the conventional shutdown method, no effective measures are taken at the die mouth and the two ends of the feed inlet of the machine head, which causes the air to enter the machine and oxidize, which ultimately promotes the thermal degradation of the residual plastic in the machine. It provides very favorable conditions for the carbonization of ultra-high molecular polyethylene liner. Due to the metal structure used in the equipment, the thermal expansion rate of the equipment is quite different from that of the plastic. The carbonized plastic has low adhesion to the metal, so it is easy to remove from the inner wall of the barrel of the equipment. , The inner wall of the machine head and the screw fall off and are finally mixed into the plastic melt, which makes the produced ultra-high molecular polyethylene liner appear more black spots on the inner and outer walls, and are prone to many quality problems such as holes or leakage.
所以模口碳化物堆积问题一直以来都是困扰工程人员的一大难题。现有技术中，主流的方法是通过设备改造来将模口碳化物定时移除，或者在注塑完成后对模口进行清洗，但并未从根源上降低模口碳化物，仍然存在模口碳化物掉入正常产品中的风险。Therefore, the problem of die-mouth carbide accumulation has always been a major problem that plagued engineers. In the prior art, the mainstream method is to periodically remove the carbide from the die through equipment modification, or to clean the die after the injection is completed, but it does not reduce the carbide from the root cause, and there is still carburization of the die. The risk of objects falling into normal products.
中国专利CN103707483A公开了一种预防造粒过程中在口模位置产生碳化物的装置，包括口模板和进气管道，所述的口模板具有模孔，进气管道的出口位于集气罩内模孔上方的位置。该技术用于聚酰胺或改性聚酰胺造粒的工艺流程中，可以防止聚酰胺融体或改性后聚酰胺熔体容易黏附在口模周围，在口模的高温和空气中氧气长时间的作用下，黏附在出料条口模周围的聚酰胺融体被氧化变色，发黄，甚至变黑。但是，该专利采用模口吹气的方式容易将碳化物吹到空气中，带来一些问题。美国专利US4124666A，公布了降低模口碳化物的方法，该方法采用在模口上端加装高压空气吹扫，以降低模口碳化物的产生。Chinese patent CN103707483A discloses a device for preventing the generation of carbides at the position of the die during the granulation process. The device includes a die plate and an air inlet pipe. The die plate has a die hole, and the outlet of the air inlet pipe is located in the inner die of the air collecting hood. The position above the hole. This technology is used in the process flow of polyamide or modified polyamide granulation, which can prevent the polyamide melt or modified polyamide melt from sticking around the die, and it will be exposed to the high temperature of the die and oxygen in the air for a long time. Under the action of, the polyamide melt adhered around the die of the discharge bar is oxidized and turned yellow or even black. However, this patent uses die-mouth blowing to easily blow the carbide into the air, which brings some problems. US Patent No. 4,124,666A, discloses a method for reducing the carbides in the die. This method uses high-pressure air blowing at the upper end of the die to reduce the production of carbides in the die.
聚合物在高温下降解时，首先生成炭自由基，然后在氧气的作用下会生成炭氧自由基和过氧化物。一般的抗氧剂(如受阻酚类抗氧剂、芳香胺类抗氧剂、亚磷酸酯类抗氧剂、硫酯 类抗氧剂等)，其抗氧化的机理是通过分解过氧化物，以降低树脂基体的被氧化程度。When the polymer is degraded at high temperature, carbon free radicals are first generated, and then carbon oxygen free radicals and peroxides are generated under the action of oxygen. General antioxidants (such as hindered phenol antioxidants, aromatic amine antioxidants, phosphite antioxidants, thioester antioxidants, etc.), the antioxidant mechanism is through the decomposition of peroxides, To reduce the degree of oxidation of the resin matrix.
本发明发现，能分解过氧化物的抗氧剂其对于长期较低温度下(100-150℃)的抗氧化效果较好，但是对于短时间的较高温度(260℃及以上，如聚酰胺加工温度某些情况下会超过330℃甚至更高)的抗氧化性能几乎为零，即使增大加入量，也无法达到降低模口碳化物的效果。较大分子的苯并呋喃酮类化合物能够捕捉炭自由基，并且能够在260℃以上的温度下也能起到优秀的抗氧化效果。The present invention found that antioxidants that can decompose peroxides have better anti-oxidation effects at lower temperatures (100-150°C) for a long time, but for short-term higher temperatures (260°C and above, such as polyamides). In some cases, the processing temperature will exceed 330°C or even higher). The oxidation resistance is almost zero. Even if the added amount is increased, the effect of reducing the carbides in the die cannot be achieved. Larger molecular benzofuranone compounds can capture carbon free radicals, and can also have an excellent antioxidant effect at temperatures above 260°C.
苯并呋喃酮类化合物是一种稳定剂、抗氧化剂，也有的化合物作为脂肪、油、食品的抗氧剂，参见中国专利申请2003801064960，但是该专利仅利用其的长期稳定性。中国专利申请2005101380935公开了一种稳定性组合物，其中，利用苯并呋喃酮作为稳定剂，并没有公开其作为抗氧剂的用途。Benzofuranone compounds are a kind of stabilizer and antioxidant, and some compounds are used as antioxidants for fats, oils and foods. See Chinese patent application 20038001064960, but this patent only uses its long-term stability. Chinese patent application 2005101380935 discloses a stabilizing composition in which benzofuranone is used as a stabilizer, and its use as an antioxidant is not disclosed.
中国专利申请2012100225970公开了一种小分子苯并呋喃酮类化合物在聚丙烯中作为抗氧剂的应用，也公开了苯并呋喃酮类化合物能够捕获碳自由基从而达到链段终止，起到抗氧化作用。但是，该专利采用的是一种小分子苯并呋喃酮类化合物，这种化合物的分子量过于小，其耐热性能不足(在260℃以上则会失去抗氧化性)。虽然其能够捕捉C自由基，但是只能在聚丙烯材料的较低的温度(一般低于200℃不超过230℃)下加工，这样就失去了抑制模口碳化物形成的功能。该化合物的抗氧化性能与其他种类化合物(如抗氧剂10989和168)相近，260℃以上的抑制模口碳化物性能的性能甚至不如上述两种抗氧化。Chinese patent application 2012100225970 discloses the application of a small molecule benzofuranone compound as an antioxidant in polypropylene. It also discloses that the benzofuranone compound can capture carbon free radicals to reach the end of the chain segment and play a role in resisting oxidation. However, this patent uses a small molecule benzofuranone compound, which has a too small molecular weight and insufficient heat resistance (it loses its oxidation resistance above 260°C). Although it can capture C free radicals, it can only be processed at a relatively low temperature of polypropylene materials (generally less than 200°C and not more than 230°C), thus losing the function of inhibiting the formation of carbides in the die. The anti-oxidation performance of this compound is similar to that of other kinds of compounds (such as antioxidants 10989 and 168), and the performance of inhibiting die carbides above 260°C is even inferior to the above two kinds of anti-oxidation.
但是，仅仅依靠添加苯并呋喃酮类化合物来改善模口碳化物，即使加大添加量，效果也是有限的。However, only relying on the addition of benzofuranone compounds to improve die carbides, even if the addition amount is increased, the effect is limited.
发明内容Summary of the invention
本发明的目的在于提供一种聚酰胺组合物，能够改善在注塑或造粒过程中模口碳化。The purpose of the present invention is to provide a polyamide composition that can improve the carbonization of the die during injection molding or pelletizing.
本发明是通过以下技术方案实现的：The present invention is realized through the following technical solutions:
一种聚酰胺组合物，按重量份计，包括以下组分：A polyamide composition, in parts by weight, comprising the following components:
聚酰胺树脂                        50-90份；Polyamide resin 50-90 copies;
苯并呋喃酮类化合物                0.01-2份；Benzofuranone compounds 0.01-2 copies;
K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐  0.5-1.5份；K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt 0.5-1.5 parts;
所述的苯并呋喃酮类化合物结构如下结构式：The structure of the benzofuranone compound is as follows:
Figure PCTCN2020124012-appb-000001
Figure PCTCN2020124012-appb-000001
其中，n＝0、1、2或3；R 1和R 2各自独立为氢或者C1-C8的烷基，R 3和R 4各自独立为氢或者C1-C6的烷基，但是不同时为C1-C6的烷基；R 5和R 6各自独立为氢或者C1-C6的烷基，但是不同时为C1-C6的烷基；R 7为氢或者羟基。 Wherein, n = 0, 1, 2 or 3; R 1 and R 2 are each independently hydrogen or C1-C8 alkyl, R 3 and R 4 are each independently hydrogen or C1-C6 alkyl, but not at the same time C1-C6 alkyl; R 5 and R 6 are each independently hydrogen or C1-C6 alkyl, but are not C1-C6 alkyl at the same time; R 7 is hydrogen or hydroxyl.
所述的聚酰胺树脂选自脂肪族聚酰胺、半芳香族聚酰胺、聚内酰胺中的至少一种。The polyamide resin is selected from at least one of aliphatic polyamides, semi-aromatic polyamides, and polylactams.
所述聚酰胺选自通过缩聚至少一种脂肪族二元羧酸与至少一种脂肪族二胺或者环二胺获得的聚酰胺，例如PA6，PA66，PA610，PA612，PA1212，PA56，PA46，MXD6、PA510；或者通过缩聚至少一种芳香族二羧酸与至少一种脂肪族二胺获得的聚酰胺，例如聚对苯二甲酰胺，据间苯二甲酰胺、聚芳酰胺，具体是PA9T、PA10T；或者通过至少一种氨基酸或内酰胺与其本身的缩聚所获得的聚酰胺，例如PA6，PA7，PA11，PA12；或者上述聚酰胺的混合物或共聚物。The polyamide is selected from polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine or cyclic diamine, such as PA6, PA66, PA610, PA612, PA1212, PA56, PA46, MXD6 , PA510; or polyamide obtained by polycondensation of at least one aromatic dicarboxylic acid and at least one aliphatic diamine, such as polyterephthalamide, according to isophthalamide, polyaramid, specifically PA9T, PA10T; or polyamide obtained by polycondensation of at least one amino acid or lactam with itself, such as PA6, PA7, PA11, PA12; or a mixture or copolymer of the above polyamides.
具体的，所述的苯并呋喃酮类化合物选自[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]苯甲酸酯、[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯、[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3-[3，5-二(第三丁基)-4-羟基-苯基]丙酸酯中的至少一种。Specifically, the benzofuranone compound is selected from [4-tertiary butyl-2-(5-tertiary butyl-2-onyl-3hydro-benzofuran-3-yl)phenyl ] Benzoate, [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3,5-bis( Tertiary butyl)-4-hydroxy-benzoate, (4-tertiary butyl-2-(5-tertiary butyl-2-keto-3hydro-benzofuran-3-yl)benzene Group]-3-[3,5-di(tertiarybutyl)-4-hydroxy-phenyl]propionate.
[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]苯甲酸酯的结构式为：The structural formula of [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]benzoate is:
Figure PCTCN2020124012-appb-000002
Figure PCTCN2020124012-appb-000002
[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯的结构式为：[4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3,5-bis(tert-butyl)- The structural formula of 4-hydroxy-benzoic acid ester is:
Figure PCTCN2020124012-appb-000003
Figure PCTCN2020124012-appb-000003
[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3-[3，5-二(第三丁基)-4-羟基-苯基]丙酸酯的结构式为：[4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3-[3,5-bis(tert-butyl The structural formula of phenyl)-4-hydroxy-phenyl]propionate is:
Figure PCTCN2020124012-appb-000004
Figure PCTCN2020124012-appb-000004
优选的，所述的苯并呋喃酮类化合物优选[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯。Preferably, the benzofuranone compound is preferably [4-tert-butyl-2-(5-tert-butyl-2-onyl-3hydro-benzofuran-3-yl)phenyl] -3,5-Di(tert-butyl)-4-hydroxy-benzoic acid ester.
所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐为K金属皂盐、Na金属皂盐、Ca金属皂盐、Mg金属皂盐、Ba金属皂盐、Zn金属皂盐、Li金属皂盐、Al金属皂盐中的至少一种。The K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt is K metal soap salt, Na metal soap salt, Ca metal soap salt, Mg metal soap salt, Ba metal soap salt, Zn metal At least one of soap salt, Li metal soap salt, and Al metal soap salt.
优选的，所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐，其中优选Zn金属皂盐和Al金属皂盐。Preferably, the said K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt, of which Zn metal soap salt and Al metal soap salt are preferred.
进一步优选的，所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐的碳原子数为28-34。Further preferably, the number of carbon atoms of the soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al metal is 28-34.
具体的，可以是褐煤酸钙、褐煤酸钠、褐煤酸铝、褐煤酸锌、硬脂酸钙、硬脂酸锌、硬脂酸铝、硬脂酸锂；褐煤酸一般是碳原子为28-34的酸。硬脂酸的碳原子数一般为18左右。Specifically, it can be calcium montanate, sodium montanate, aluminum montanate, zinc montanate, calcium stearate, zinc stearate, aluminum stearate, lithium stearate; montanic acid generally has a carbon atom of 28- 34 acid. The number of carbon atoms of stearic acid is generally about 18.
K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐一般是作为润滑剂，但是，本发明发现，当与苯并呋喃酮类化合物同时加入时，能够起到成核剂的作用，协同之下进一步改善了模口碳化物的生成，这是加入其他润滑剂所不能达到的。K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐加入量过多也会导致聚酰胺组合物的其他性能(如力学性能)的下降。K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salts are generally used as lubricants. However, the present invention has found that when added simultaneously with benzofuranone compounds, they can act as nucleating agents. Under the synergy, the formation of carbides in the die mouth is further improved, which cannot be achieved by adding other lubricants. Too much addition of the soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al metal will also lead to a decrease in other properties (such as mechanical properties) of the polyamide composition.
如需要提高聚酰胺组合物的强度，可以添加玻璃纤维。按重量份计，还包括0-50份的玻璃纤维；所述的玻璃纤维选自E玻璃、H玻璃、R,S玻璃、D玻璃、C玻璃、石英玻璃中的至少一种。If it is necessary to increase the strength of the polyamide composition, glass fiber can be added. In parts by weight, it also includes 0-50 parts of glass fiber; the glass fiber is selected from at least one of E glass, H glass, R, S glass, D glass, C glass, and quartz glass.
上述的聚酰胺组合物的制备方法，包括以下步骤：将聚酰胺树脂、苯并呋喃酮类化合物、 K/Na/Ca/Mg/Ba/Zn/Li金属的皂盐混合均匀，再通过双螺杆挤出机(侧喂玻璃纤维)挤出造粒，得到聚酰胺组合物。The preparation method of the above polyamide composition includes the following steps: mixing the polyamide resin, the benzofuranone compound, and the soap salt of K/Na/Ca/Mg/Ba/Zn/Li metal uniformly, and then passing it through a twin screw The extruder (side-fed glass fiber) is extruded and pelletized to obtain a polyamide composition.
本发明与现有技术相比，具有如下有益效果Compared with the prior art, the present invention has the following beneficial effects
相对于常用的抗氧剂(如受阻酚类抗氧剂、芳香胺类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂等)，本发明利用苯并呋喃酮类化合物完全能够耐受在熔融的高温，其捕捉碳自由基的能力协同K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐的成核性，能够改善模口碳化程度。Compared with commonly used antioxidants (such as hindered phenol antioxidants, aromatic amine antioxidants, phosphite antioxidants, thioester antioxidants, etc.), the present invention uses benzofuranone compounds to completely It can withstand the high temperature of melting, and its ability to capture carbon radicals cooperates with the nucleation of the soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al, which can improve the degree of carbonization of the die.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明所用原料来源于市售产品。The raw materials used in the present invention are derived from commercially available products.
PA66：PA66EP-158，浙江华峰集团；PA66: PA66EP-158, Zhejiang Huafeng Group;
PA6：HY2800A，海阳化纤集团；PA6: HY2800A, Haiyang Chemical Fiber Group;
PA10T：VESTAMID HTplus M1000，赢创工业集团；PA10T: VESTAMID HTplus M1000, Evonik Industries Group;
PA-MXD6：RENY 1002H，三菱化学株式会社；PA-MXD6: RENY 1002H, Mitsubishi Chemical Corporation;
苯并呋喃酮类化合物Ⅰ：[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]苯甲酸酯；Benzofuranone compounds I: [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]benzoate;
苯并呋喃酮类化合物Ⅱ：[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯；Benzofuranone compounds II: [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3,5- Di(tertiary butyl)-4-hydroxy-benzoic acid ester;
苯并呋喃酮类化合物Ⅲ：[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3-[3，5-二(第三丁基)-4-羟基-苯基]丙酸酯；Benzofuranone compounds III: [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3-[3 , 5-Di(tert-butyl)-4-hydroxy-phenyl]propionate;
苯并呋喃酮类化合物N：3,4-二丁基-5-(2,4-二甲基苯基)苯并呋喃-2(3H)-酮；Benzofuranone compound N: 3,4-dibutyl-5-(2,4-dimethylphenyl)benzofuran-2(3H)-one;
受阻酚类抗氧剂：Irganox 1098，巴斯夫中国有限公司；Hindered phenolic antioxidant: Irganox 1098, BASF China Co., Ltd.;
亚磷酸酯抗氧剂：Irganox 168，巴斯夫中国有限公司；Phosphite antioxidant: Irganox 168, BASF China Co., Ltd.;
褐煤酸钙：CAV102，Clariant中国有限公司；Calcium montanate: CAV102, Clariant China Co., Ltd.;
褐煤酸钠：NAV101，Clariant中国有限公司；Sodium montanate: NAV101, Clariant China Co., Ltd.;
褐煤酸锌：化学纯，上海阿拉丁生化科技股份有限公司；Zinc montanate: chemically pure, Shanghai Aladdin Biochemical Technology Co., Ltd.;
褐煤酸铝：上海阿拉丁生化科技股份有限公司；Aluminum montanate: Shanghai Aladdin Biochemical Technology Co., Ltd.;
硬脂酸钙：上海阿拉丁生化科技股份有限公司；Calcium stearate: Shanghai Aladdin Biochemical Technology Co., Ltd.;
脂肪酸酯1：LOXIOL G 32，EmeryOleochemicals LLC；Fatty acid ester 1: LOXIOL G 32, EmeryOleochemicals LLC;
脂肪酸酯2：Loxiol EP-PTS，EmeryOleochemicals LLC；Fatty acid ester 2: Loxiol EP-PTS, EmeryOleochemicals LLC;
各项性能测试方法：Various performance test methods:
(1)观测模口出现碳化物时间：开机后观测模口出现碳化物的时间。(1) Observe the time for the appearance of carbides in the die: Observe the time for the appearance of carbides in the die after starting the machine.
实施例和对比例聚酰胺组合物的制备方法：将聚酰胺树脂、苯并呋喃酮类化合物(或其他抗氧剂)、K/Na/Ca/Mg/Ba/Zn/Li金属的皂盐(或脂肪酸酯1、脂肪酸酯2)混合均匀，再通过双螺杆挤出机挤出造粒，得到聚酰胺组合物；其中，双螺杆挤出机的螺杆长径比为40:1，螺筒温度为250-330℃，螺杆转速为300～450rpm。The preparation method of the polyamide composition of the embodiment and the comparative example: the polyamide resin, the benzofuranone compound (or other antioxidant), the soap salt of K/Na/Ca/Mg/Ba/Zn/Li metal ( Or fatty acid ester 1 and fatty acid ester 2) are mixed uniformly, and then extruded and pelletized by a twin-screw extruder to obtain a polyamide composition; wherein, the screw length-to-diameter ratio of the twin-screw extruder is 40:1, The barrel temperature is 250-330°C, and the screw speed is 300-450 rpm.
表1：实施例1-4聚酰胺组合物各组分配比(重量份)及测试结果Table 1: The distribution ratios (parts by weight) and test results of the polyamide compositions of Examples 1-4
 To 实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4
PA6PA6 8080  To  To  To
PA66PA66  To 8080  To  To
PA10TPA10T  To  To 8080  To
MXD6MXD6  To  To  To 8080
苯并呋喃酮类化合物ⅠBenzofuranone compounds Ⅰ 0.20.2 0.050.05 0.40.4 1.21.2
褐煤酸钙Calcium montanate 0.50.5 0.80.8 1.01.0 1.51.5
模口出现碳化物时间，minCarbide appearance time in the die, min 300300 330330 350350 380380
注：PA6、PA66、PA10T、MXD6中，PA6最容易形成模口碳化物。Note: Among PA6, PA66, PA10T, and MXD6, PA6 is the easiest to form die carbide.
表2：实施例5-8组合物各组分配比(重量份)及测试结果Table 2: Distribution ratios (parts by weight) and test results of each group of the compositions of Examples 5-8
 To 实施例5Example 5 实施例6Example 6 实施例7Example 7 实施例8Example 8 实施例9Example 9 实施例10Example 10
PA6PA6 8080 8080 8080 8080 8080 8080
苯并呋喃酮类化合物ⅠBenzofuranone compounds Ⅰ 0.20.2 0.20.2 0.20.2 0.20.2  To  To
苯并呋喃酮类化合物ⅡBenzofuranone compounds Ⅱ  To  To  To  To 0.20.2  To
苯并呋喃酮类化合物ⅢBenzofuranone compounds Ⅲ  To  To  To  To  To 0.20.2
褐煤酸钠Sodium montanate 0.50.5  To  To  To 0.50.5 0.50.5
褐煤酸锌Zinc montanate  To 0.50.5  To  To  To  To
褐煤酸铝Aluminum montanate  To  To 0.50.5  To  To  To
硬脂酸钙Calcium stearate  To  To  To 0.50.5  To  To
模口出现碳化物时间，minCarbide appearance time in the die, min 360360 450450 500500 230230 600600 430430
从实施例5/9/10可知，优选[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯(Ⅱ)。It can be seen from Example 5/9/10 that [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3-yl)phenyl]-3 is preferred , 5-Di(tert-butyl)-4-hydroxy-benzoic acid ester (II).
从实施例1/5/6/7/8可知，优选铝皂盐、锌皂盐；更优选碳原子数为28-34的金属皂盐。It can be seen from Example 1/5/6/7/8 that aluminum soap salts and zinc soap salts are preferred; metal soap salts having 28-34 carbon atoms are more preferred.
表3：对比例1-7组合物各组分配比(重量份)及测试结果Table 3: Distribution ratios (parts by weight) and test results of the compositions of Comparative Examples 1-7
Figure PCTCN2020124012-appb-000005
Figure PCTCN2020124012-appb-000005
Figure PCTCN2020124012-appb-000006
Figure PCTCN2020124012-appb-000006
表4：对比例8组合物各组分配比(重量份)及测试结果Table 4: Distribution ratio (parts by weight) and test results of each group of the composition of Comparative Example 8
 To 对比例8Comparative example 8
PA6PA6 8080
苯并呋喃酮类化合物NBenzofuranone compounds N 0.20.2
褐煤酸钠Sodium montanate 0.50.5
模口出现碳化物时间，minCarbide appearance time in the die, min 7070
从对比例1-3可知，常规的抗氧剂和润滑剂组合，即使用量增加，也是不能有效改善模口碳化物的形成。It can be seen from Comparative Examples 1-3 that the conventional combination of antioxidants and lubricants, even if the dosage is increased, cannot effectively improve the formation of carbides in the die.
从对比例4/5/7可知，苯并呋喃酮类化合物和金属的皂盐需要协同作用才能有效改善模口碳化物的形成。It can be seen from the comparative example 4/5/7 that the benzofuranone compound and the metal soap salt need a synergistic effect to effectively improve the formation of carbides in the die.
从对比例6可知，金属的皂盐的加入量也是本发明的重点，加入量过少，改善模口碳化物的效果不足。It can be seen from Comparative Example 6 that the addition amount of the metal soap salt is also the focus of the present invention. If the addition amount is too small, the effect of improving the carbides in the die is insufficient.
从对比例8可知，小分子的苯并呋喃酮类化合物其改善模口碳化物性能不足，并且因其受高温容易分解，相比于其他类型抗氧剂，其出现碳化物时间反而更早。It can be seen from Comparative Example 8 that small-molecule benzofuranone compounds have insufficient performance in improving mold carbides and are easily decomposed by high temperature. Compared with other types of antioxidants, their carbides appear earlier.

Claims (9)

  1. 一种聚酰胺组合物，其特征在于，按重量份计，包括以下组分：A polyamide composition, characterized in that, in parts by weight, it comprises the following components:
    聚酰胺树脂                        50-90份；Polyamide resin 50-90 copies;
    苯并呋喃酮类化合物                0.01-2份；Benzofuranone compounds 0.01-2 copies;
    K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐  0.5-1.5份；K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt 0.5-1.5 parts;
    所述的苯并呋喃酮类化合物结构如下结构式：The structure of the benzofuranone compound is as follows:
    Figure PCTCN2020124012-appb-100001
    Figure PCTCN2020124012-appb-100001
    其中，n＝0、1、2或3；R 1和R 2各自独立为氢或者C1-C8的烷基，R 3和R 4各自独立为氢或者C1-C6的烷基，但是不同时为C1-C6的烷基；R 5和R 6各自独立为氢或者C1-C6的烷基，但是不同时为C1-C6的烷基；R 7为氢或者羟基。 Wherein, n = 0, 1, 2 or 3; R 1 and R 2 are each independently hydrogen or C1-C8 alkyl, R 3 and R 4 are each independently hydrogen or C1-C6 alkyl, but not at the same time C1-C6 alkyl; R 5 and R 6 are each independently hydrogen or C1-C6 alkyl, but are not C1-C6 alkyl at the same time; R 7 is hydrogen or hydroxyl.
  2. 根据权利要求1所述的聚酰胺组合物，其特征在于，所述聚酰胺选自通过缩聚至少一种脂肪族二元羧酸与至少一种脂肪族二胺或者环二胺获得的聚酰胺，或者通过缩聚至少一种芳香族二羧酸与至少一种脂肪族二胺获得的聚酰胺，或者通过至少一种氨基酸或内酰胺与其本身的缩聚所获得的聚酰胺，或者上述聚酰胺的混合物或共聚物。The polyamide composition according to claim 1, wherein the polyamide is selected from polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine or cyclic diamine, Or polyamides obtained by polycondensation of at least one aromatic dicarboxylic acid and at least one aliphatic diamine, or polyamides obtained by polycondensation of at least one amino acid or lactam with itself, or a mixture of the aforementioned polyamides or Copolymer.
  3. 根据权利要求2所述的聚酰胺组合物，其特征在于，所述的聚酰胺树脂选自PA6、PA66、PA56、PA610、PA612、PA510、PA46、PA9T、PA10T、PA66/6T、PA66/10T、MXD6中的至少一种。The polyamide composition according to claim 2, wherein the polyamide resin is selected from PA6, PA66, PA56, PA610, PA612, PA510, PA46, PA9T, PA10T, PA66/6T, PA66/10T, At least one of MXD6.
  4. 根据权利要求1所述的聚酰胺组合物，其特征在于，所述的苯并呋喃酮类化合物选自[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]苯甲酸酯、[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯、[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3-[3，5-二(第三丁基)-4-羟基-苯基]丙酸酯中的至少一种。The polyamide composition according to claim 1, wherein the benzofuranone compound is selected from [4-tertiary butyl-2-(5-tertiary butyl-2-onyl- 3-Hydro-benzofuran-3-yl)phenyl]benzoate, [4-tert-butyl-2-(5-tert-butyl-2-keto-3hydro-benzofuran-3) -Yl)phenyl]-3,5-bis(tert-butyl)-4-hydroxy-benzoate, [4-tert-butyl-2-(5-tert-butyl-2-keto -At least one of 3-hydro-benzofuran-3-yl)phenyl]-3-[3,5-di(tertiarybutyl)-4-hydroxy-phenyl]propionate.
  5. 根据权利要求4所述的聚酰胺组合物，其特征在于，所述的苯并呋喃酮类化合物选优选[4-第三丁基-2-(5-第三丁基-2-酮基-3氢-苯并呋喃-3-基)苯基]-3，5-二(第三丁基)-4-羟基-苯甲酸酯。The polyamide composition of claim 4, wherein the benzofuranone compound is preferably [4-tertiary butyl-2-(5-tertiary butyl-2-onyl- 3-Hydro-benzofuran-3-yl)phenyl]-3,5-bis(tert-butyl)-4-hydroxy-benzoate.
  6. 根据权利要求1所述的聚酰胺组合物，其特征在于，所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐为K金属皂盐、Na金属皂盐、Ca金属皂盐、Mg金属皂盐、Ba金属皂盐、Zn金 属皂盐、Li金属皂盐、Al金属皂盐中的至少一种；优选的，所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐选自Zn金属皂盐和Al金属皂盐。The polyamide composition according to claim 1, wherein the K/Na/Ca/Mg/Ba/Zn/Li/Al metal soap salt is K metal soap salt, Na metal soap salt, Ca At least one of metal soap salt, Mg metal soap salt, Ba metal soap salt, Zn metal soap salt, Li metal soap salt, and Al metal soap salt; preferably, the K/Na/Ca/Mg/Ba/ The soap salt of Zn/Li/Al metal is selected from Zn metal soap salt and Al metal soap salt.
  7. 根据权利要求6所述的聚酰胺组合物，其特征在于，所述的K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐的碳原子数为28-34。The polyamide composition according to claim 6, wherein the number of carbon atoms of the soap salt of K/Na/Ca/Mg/Ba/Zn/Li/Al is 28-34.
  8. 根据权利要求1所述的聚酰胺组合物，其特征在于，按重量份计，还包括0-50份的玻璃纤维；所述的玻璃纤维选自E玻璃、H玻璃、R,S玻璃、D玻璃、C玻璃、石英玻璃中的至少一种。The polyamide composition according to claim 1, characterized in that it further comprises 0-50 parts by weight of glass fiber; the glass fiber is selected from E glass, H glass, R, S glass, D At least one of glass, C glass, and quartz glass.
  9. 权利要求8所述的聚酰胺组合物的制备方法，其特征在于，包括以下步骤：将聚酰胺树脂、苯并呋喃酮类化合物、K/Na/Ca/Mg/Ba/Zn/Li/Al金属的皂盐混合均匀，再通过双螺杆挤出机(侧喂玻璃纤维)挤出造粒，得到聚酰胺组合物。The preparation method of the polyamide composition according to claim 8, characterized in that it comprises the following steps: combining polyamide resin, benzofuranone compound, K/Na/Ca/Mg/Ba/Zn/Li/Al metal The soap salt is uniformly mixed, and then extruded and granulated through a twin-screw extruder (side-feeding glass fiber) to obtain a polyamide composition.
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Publication number Priority date Publication date Assignee Title
CN111117216B (en) * 2019-12-19 2021-09-17 金发科技股份有限公司 Polyamide composition and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004623A1 (en) * 1998-11-25 2000-05-31 Great Lakes Chemical Corporation Aryl thioacetals useful as stabilizers in polymeric materials
CN1407005A (en) * 2001-09-11 2003-04-02 西巴特殊化学品控股有限公司 Synthetic polymer stable method
US20050228109A1 (en) * 2004-04-07 2005-10-13 Tapan Chandra Thermoplastic compositions with improved paint adhesion
CN102372921A (en) * 2011-10-10 2012-03-14 金发科技股份有限公司 Heat resistant polyamide composite and applications thereof
CN102675269A (en) * 2011-03-17 2012-09-19 奇钛科技股份有限公司 Benzofuran derivatives and uses thereof
CN105949763A (en) * 2016-05-16 2016-09-21 上海日之升科技有限公司 Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition
CN105968339A (en) * 2015-03-10 2016-09-28 赢创德固赛有限公司 Antioxidants for producing low-emission PUR systems
CN111117216A (en) * 2019-12-19 2020-05-08 金发科技股份有限公司 Polyamide composition and preparation method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4079334B2 (en) * 2004-11-25 2008-04-23 旭化成ケミカルズ株式会社 Resin composition suitable for sheet molding
CN102108208B (en) * 2009-12-29 2013-03-20 合肥杰事杰新材料股份有限公司 High-strength flame-retardant polyamide composite material and preparation method
CN103059556A (en) * 2011-10-19 2013-04-24 合肥杰事杰新材料股份有限公司 Polyamide composition and preparation method thereof
CN103013099A (en) * 2012-12-03 2013-04-03 合肥杰事杰新材料股份有限公司 High-flowability long glass fiber reinforced nylon 6 material and preparation method thereof
CN103665848B (en) * 2013-11-28 2016-03-30 方万漂 A kind of polythene/nylon 6 mixing modification barrier material
CN106479169A (en) * 2015-08-27 2017-03-08 合肥杰事杰新材料股份有限公司 A kind of low abnormal smells from the patient, low distribute, halogen-free flame-resistant high-temperature-resistant nylon and preparation method thereof
CN106280422A (en) * 2016-08-30 2017-01-04 宁波伊德尔新材料有限公司 A kind of low abnormal smells from the patient fire-retardant Nylon 6 composite and preparation method thereof
CA3082349A1 (en) * 2017-11-14 2019-05-23 Basf Se Polycarbonate compositions
CN110256844A (en) * 2019-07-03 2019-09-20 徐州腾飞工程塑料有限公司 A kind of 3D printing color inhibition nylon composite materials and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004623A1 (en) * 1998-11-25 2000-05-31 Great Lakes Chemical Corporation Aryl thioacetals useful as stabilizers in polymeric materials
CN1407005A (en) * 2001-09-11 2003-04-02 西巴特殊化学品控股有限公司 Synthetic polymer stable method
US20050228109A1 (en) * 2004-04-07 2005-10-13 Tapan Chandra Thermoplastic compositions with improved paint adhesion
CN102675269A (en) * 2011-03-17 2012-09-19 奇钛科技股份有限公司 Benzofuran derivatives and uses thereof
CN102372921A (en) * 2011-10-10 2012-03-14 金发科技股份有限公司 Heat resistant polyamide composite and applications thereof
CN105968339A (en) * 2015-03-10 2016-09-28 赢创德固赛有限公司 Antioxidants for producing low-emission PUR systems
CN105949763A (en) * 2016-05-16 2016-09-21 上海日之升科技有限公司 Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition
CN111117216A (en) * 2019-12-19 2020-05-08 金发科技股份有限公司 Polyamide composition and preparation method thereof

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