WO2021120863A1 - Composition de polyamide et procédé pour sa préparation - Google Patents

Composition de polyamide et procédé pour sa préparation 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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WO
WIPO (PCT)
Prior art keywords
soap salt
metal soap
butyl
polyamide composition
tert
Prior art date
Application number
PCT/CN2020/124012
Other languages
English (en)
Chinese (zh)
Inventor
郑一泉
叶南飚
何勇
丁超
冯德才
金雪峰
戴剑
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Publication of WO2021120863A1 publication Critical patent/WO2021120863A1/fr

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Classifications

    • 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

L'invention concerne une composition de polyamide qui peut améliorer efficacement la formation d'un carbure au niveau de l'orifice d'une filière pendant le moulage par injection ou la granulation. La présente invention améliore la formation d'un carbure au niveau de l'orifice d'une filière pendant le moulage par injection grâce à l'effet synergique d'un composé de benzofuranone et d'un sel de savon des métaux suivants : K/Na/Ca/Mg/Ba/Zn/Li/Al. En particulier, un composé de benzofuranone a pour fonction de capturer un radical libre C dans le polyamide, et le sel de savon des métaux K/Na/Ca/Mg/Ba/Zn/Li/Al peut avoir un effet de nucléation et, conjointement, ils empêchent la température locale pendant le moulage par injection d'être trop élevée, ce qui conduit à la formation d'un carbure et ce qui, en particulier, empêche l'adhérence de celui-ci à l'orifice d'une filière.
PCT/CN2020/124012 2019-12-19 2020-10-27 Composition de polyamide et procédé pour sa préparation WO2021120863A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911318048.6A CN111117216B (zh) 2019-12-19 2019-12-19 一种聚酰胺组合物及其制备方法
CN201911318048.6 2019-12-19

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WO2021120863A1 true WO2021120863A1 (fr) 2021-06-24

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WO (1) WO2021120863A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111117216B (zh) * 2019-12-19 2021-09-17 金发科技股份有限公司 一种聚酰胺组合物及其制备方法

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CN105949763A (zh) * 2016-05-16 2016-09-21 上海日之升科技有限公司 一种环保型良外观热水稳定聚酰胺组合物及其制备方法
CN105968339A (zh) * 2015-03-10 2016-09-28 赢创德固赛有限公司 用于制备低排放pur 体系的抗氧化剂
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1004623A1 (fr) * 1998-11-25 2000-05-31 Great Lakes Chemical Corporation Aryl thioacétales utilisables comme stabilisateurs pour matériaux polymériques
CN1407005A (zh) * 2001-09-11 2003-04-02 西巴特殊化学品控股有限公司 合成聚合物的稳定方法
US20050228109A1 (en) * 2004-04-07 2005-10-13 Tapan Chandra Thermoplastic compositions with improved paint adhesion
CN102675269A (zh) * 2011-03-17 2012-09-19 奇钛科技股份有限公司 苯并呋喃衍生物及其应用
CN102372921A (zh) * 2011-10-10 2012-03-14 金发科技股份有限公司 一种耐热聚酰胺组合物及其应用
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CN105949763A (zh) * 2016-05-16 2016-09-21 上海日之升科技有限公司 一种环保型良外观热水稳定聚酰胺组合物及其制备方法
CN111117216A (zh) * 2019-12-19 2020-05-08 金发科技股份有限公司 一种聚酰胺组合物及其制备方法

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