WO2026020423A1 - Composition de polyamide - Google Patents

Composition de polyamide

Info

Publication number
WO2026020423A1
WO2026020423A1 PCT/CN2024/107597 CN2024107597W WO2026020423A1 WO 2026020423 A1 WO2026020423 A1 WO 2026020423A1 CN 2024107597 W CN2024107597 W CN 2024107597W WO 2026020423 A1 WO2026020423 A1 WO 2026020423A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
weight
parts
fraction
cycloaliphatic
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/CN2024/107597
Other languages
English (en)
Inventor
Lixia Wang
Varun DANKE
Fei TENG
Reinhard Linemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Priority to PCT/CN2024/107597 priority Critical patent/WO2026020423A1/fr
Priority to PCT/CN2025/104396 priority patent/WO2026021148A1/fr
Publication of WO2026020423A1 publication Critical patent/WO2026020423A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

  • the invention relates to a homogeneous amorphous composition based on cycloaliphatic polyamide having improved chemical resistance.
  • polymer blending is a known approach to modify properties. Educated blending however leads to certain synergies which can exploited to achieve surprising improvements over standard materials. Polyamide blending is a known state of the art and a significant amount of literature can be found.
  • US2018327592A1 describes a composition having improved dimensional stability due to reduced water uptake and comprising an amorphous polyamide or a mixture of amorphous polyamides, and a semi-crystalline polyamide for which the average number of carbon atoms relatively to the nitrogen atom is greater than or equal to 8 or a mixture of semi-crystalline polyamides wherein the average number of carbon atoms relatively to the nitrogen atom of each of the semi-crystalline polyamides is greater than or equal to 8. It is mentioned that when the amorphous polyamide is PAMACM. 12, the semi-crystalline polyamide is not a PA 12. No information is provided on optical properties or chemical resistance.
  • US20230033437A1 relates to black-colored polyamide molding compounds based on transparent polyamides with good weathering resistance.
  • Such molding PA compounds have very many applications in industry for preparing articles selected from the group consisting of interior and exterior parts for automobiles, motorcycles, camping vehicles or caravans, building and decorative structural frames, operating knobs or levers, covers, visible surfaces, backlit components, screens of cell phones, tablets, housings of electronic devices, decorative parts in vehicles, household appliances, containers, vehicle keys, leisure and outdoor articles.
  • US11466153B2 discloses polyamide moulding compounds which are based on mixture of specific amorphous or microcrystalline polyamides and specific partially crystalline polyamides and are distinguished by a very good stress crack resistance and at the same time by very good optical properties, in particular a high light transmission and a low haze. Furthermore, it is proven that blends of an amorphous polyamide and the frequently used partially crystalline polyamide 12 in contrast produce poorer properties.
  • US2018/0100064A1 relates to polyamide moulding compounds which are reinforced with a glass filler and have a low haze. These polyamide moulding compounds are based on amorphous copolyamides, precisely one amorphous copolyamide being contained in a polyamide moulding compound. The addition of partially crystalline polyamides is intended in fact to be possible but not obligatory, in order to achieve the desired optical properties.
  • US9416233B2 provides composite polyamide fine particles comprising a polyamide (A1) having a melting point or a glass transition temperature higher than 100°C, and a polymer (A2) different from the polyamide (A1) , wherein the composite polyamide fine particles have a dispersion structure in which a plurality of domains each having a particle diameter of 0.05 to 100 ⁇ m whose main component is the polymer (A2) are dispersed in a matrix having the polyamide (A1) as its main component.
  • the composite polyamide fine particles have the effect of improving the fracture toughness significantly.
  • CN117430947A discloses a polyamide composite material with chemical resistance and low internal stress, characterized by comprising the following components in parts by weight:
  • the polymerizable monomer of the main chain of the transparent polyamide comprises a C12 monomer, and the C12 monomer is dodecanedioic acid or 12-aminododecanoic acid;
  • the crystalline polyamide is at least one of PA612, PA1012, PA12 or PA1212, and has a fusion enthalpy ⁇ H m ⁇ 25 J/g during a second heating in DSC.
  • the invention relates to the use of at least one linear aliphatic polyamide having an average of from 9 to 12 C atoms in the monomer units in a homogeneous amorphous composition
  • a homogeneous amorphous composition comprising at least one cycloaliphatic polyamide based on a cycloaliphatic diamine having 10-20 carbon atoms and an aliphatic dicarboxylic acid having 8-18 carbon atoms for improving chemical resistance of said composition.
  • the present invention is based on the discovery that the introduction of at least one linear aliphatic polyamide in a homogeneous amorphous composition based on cycloaliphatic polyamide, gives the possibility of improving its chemical resistance. At the same time, said introduction makes lower haze and higher transparency possible.
  • a homogeneous amorphous composition in the sense of the present invention, refers to an amorphous composition having only one single glassy transition temperature with or without a melting temperature after the introduction of the at least one linear aliphatic polyamide into the cycloaliphatic polyamide.
  • the enthalpy of crystallization during the cooling step at a rate of 20°C/min in Differential Scanning Calorimetry (DSC) measured according to the standard ISO 11357 is less than 15 J/g, in particular less than 5 J/g.
  • composition comprising:
  • polyamide fraction consisting of:
  • the parts of component a) in the polyamide fraction is in the range of 60 to 95%by weight, relative to the total weight of the polyamide fraction, and the parts of component b) in the polyamide fraction is in the range of 5 to 40%by weight.
  • the parts of component a) in the polyamide fraction is in the range of 75 to 90%by weight, relative to the total weight of the polyamide fraction, and the parts of component b) in the polyamide fraction is in the range of 10 to 25%by weight.
  • the first embodiment provides a homogeneous amorphous composition
  • a homogeneous amorphous composition comprising, based on the total weight of the composition, at least 50%by weight, preferably at least 60%by weight, particularly preferably at least 70%by weight, with particular preference at least 80%by weight and very particularly preferably at least 90%by weight, or at least 95%by weight, of a polyamide fraction which consists of
  • the composition is in a form selected from the group consisting of a pellet mixture, a powder mixture and a blend.
  • the components according to a) and b) in each case in the form of pellets, are combined and are mechanically mixed –in the form of solids mixture.
  • the pellets may additionally comprise other additives which are described in more detail below.
  • the pellet mixture may be processed through melting, mixing and shaping to give a moulding. It is advisable here to mix the melt thoroughly, in order to obtain a homogeneous moulding. Suitable mixing assemblies include kneaders or extruders; the processing to give the moulding may take place through injection moulding, extrusion, compression processes or rolling.
  • the components a) and, respectively, b) in each case in the form of powder, are combined and mechanically mixed.
  • the powder here can also comprise, alongside the component according to a) and, respectively b) , other additions which are described in more detail below.
  • the powder mixture can be processed through melting, mixing and shaping to give a moulding. Here again, it is advisable to mix the melt thoroughly, in order to obtain a homogeneous moulding.
  • the composition may moreover also be in the form of a blend produced through mixing in the melt, discharge and comminution.
  • blend according to the present invention includes multiphase mixtures where the individual components are present in the form of domains, and also mixtures where the compatibility of the individual components is so high that these have become mixed on the molecular scale. Another term often used synonymously for such a blend is alloy.
  • the mixing in the melt may be conducted in a kneading assembly as is conventionally known, the discharge generally takes place in the form of strand and the methods generally used for comminution include granulation, breaking or grinding.
  • the blend according to the present invention may also comprise, in addition to the component according to a) and, respectively b) , other additions which are described in more detail below.
  • the cycloaliphatic polyamide is PACM/MACM-based.
  • the cycloaliphatic polyamide is selected from the group consisting of:
  • PA MACM12 polyamide made of bis (3-methyl-4-aminocyclohexyl) methane and dodecanedioic acid
  • PA PACM12 polyamide
  • PA PACMX describes a polyamide composed of monomer units which derive from bis (4-aminocyclohexyl) methane (PACM) and a linear dicarboxylic acid having X carbon atoms.
  • PA MACMX denotes a polyamide made of monomer units which derive from bis- (3-methyl-4-aminocyclohexyl) -methane (MACM) and from a linear dicarboxylic acid having X carbon atoms.
  • said linear dicarboxylic acid having X carbon atoms may be:
  • X 8: octanedioic acid (suberic acid) ;
  • X 9: nonanedioic acid (azelaic acid) ;
  • X 10: decanedioic acid (sebacic acid) ;
  • X 13: tridecanedioic acid (brassylic acid) ;
  • X 14: tetradecanedioic acid
  • X 16: hexadecanedioic acid
  • X 18: octadecanedioic acid.
  • the PA PACMX is typically produced from PACM and the dicarboxylic acid by polycondensation in the melt according to known processes. However, derivatives thereof may also be employed, for example the diisocyanate which derives from PACM, or a dicarboxylic diester.
  • PACM exists as a mixture of cis, cis, cis, trans and trans, trans isomers. It is commercially available with various isomer ratios.
  • the trans, trans-isomer content of the PACM or of the derivative used thereof is from 5 to 30%.
  • PA PACMX is a PA PACM12 in which the trans, trans isomer content of the PACM or of the employed derivative thereof is from 5 to 30%.
  • the linear aliphatic polyamide b) according to the present invention has on average from 9 to 12 C atoms in the individual monomer units. It may be produced from a combination of diamine and dicarboxylic acid, from ⁇ -aminocarboxylic acid and/or from the corresponding lactam.
  • the monomer units may derive from lactam, ⁇ -aminocarboxylic acid, diamine and, respectively, dicarboxylic acid and non-limiting examples of the polyamides include the following.
  • suitable polyamides of the invention may include copolyamides which, on the basis of suitable comonomer selection, comply with the condition that the monomer units comprise an average of from 9 to 12 C atoms, for example the copolyamide made of laurolactam, decanediamine and dodecanedioic acid (co-PA12/1012) .
  • the linear aliphatic polyamide b) is selected from the group consisting of PA12, PA1012.
  • the composition of the invention may further comprise other constituents.
  • further constituents may include but are not limited to flame retardants, stabilizers, plasticizers, glass fibers, fillers, antistatic agents, dyes, pigments, mould-release agents, flow aids, compatibilizers and impact modifiers.
  • the total quantity of these other constituents is at most 50%by weight, preferably at most 40%by weight, particularly preferably at most 30%by weight, with particular preference at most 20%by weight and very particularly preferably at most 10%by weight, or at most 5%by weight of the total composition.
  • the other constituent is a stabilizer
  • Suitable stabilizers may include but are not limited to tris (2, 4-ditertbutylphenyl) phosphite.
  • PAPACM12 amorphous polyamide produced from bis (4-aminocyclohexyl) methane with about 20%content of trans, trans-stereoisomer, and also dodecanedioic acid.
  • TR90 natural is PAMACM12 from EMS, amorphous.
  • CW1265 NC is PA1012 commercially available from Evonik Industries AG.
  • L1901 NC is PA12 commercially available from Evonik Industries AG.
  • L1600 NC is PA12 commercially available from Evonik Industries AG.
  • D16 is PA612 commercially available from Evonik Industries AG.
  • 168 is tris (2, 4-ditertbutylphenyl) phosphite from BASF.
  • C1 represents Comparative Example 1. Accordingly, C2 represents Comparative Example 2.
  • Haze and transparency were measured according to the national standard GB/T 2410-2008 by a transmittance-haze tester on a 1 mm thick square plate.
  • Injection molded parts especially transparent parts such as lenses need to have resistance against common cleaning solutions which often contain ethanol. In order to ensure sufficient resistance to ethanol, the following test was performed.
  • the 1 mm thick square plate was immersed in an ethanol solution with a concentration of 99.6%, and left to stand for 1 h. Then, it was taken out, and tested by a transmittance-haze tester according to the national standard GB/T 2410-2008 to obtain the data of transmittance and haze. The results are summarized in Table 2.

Landscapes

  • 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

L'invention concerne une composition, comprenant : au moins 50% en poids d'une fraction de polyamide; la fraction polyamide étant constituée de : a) de 50 à 95 parties en poids d'au moins un polyamide cycloaliphatique à base d'une diamine cycloaliphatique ayant de 10 à 20 atomes de carbone et d'un acide dicarboxylique aliphatique ayant de 8 à 18 atomes de carbone; et b) de 50 à 5 parties en poids d'au moins un polyamide aliphatique linéaire ayant une moyenne de 9 à 12 atomes de C dans les unités monomères, la somme des parties en poids de a) et b) étant de 100.
PCT/CN2024/107597 2024-07-25 2024-07-25 Composition de polyamide Pending WO2026020423A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2024/107597 WO2026020423A1 (fr) 2024-07-25 2024-07-25 Composition de polyamide
PCT/CN2025/104396 WO2026021148A1 (fr) 2024-07-25 2025-06-27 Composition de polyamide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/107597 WO2026020423A1 (fr) 2024-07-25 2024-07-25 Composition de polyamide

Publications (1)

Publication Number Publication Date
WO2026020423A1 true WO2026020423A1 (fr) 2026-01-29

Family

ID=92543227

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2024/107597 Pending WO2026020423A1 (fr) 2024-07-25 2024-07-25 Composition de polyamide
PCT/CN2025/104396 Pending WO2026021148A1 (fr) 2024-07-25 2025-06-27 Composition de polyamide

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/CN2025/104396 Pending WO2026021148A1 (fr) 2024-07-25 2025-06-27 Composition de polyamide

Country Status (1)

Country Link
WO (2) WO2026020423A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2460858A1 (fr) * 2010-12-02 2012-06-06 EMS-Patent AG Masses de formage polyamides à base de mélanges de copolyamides transparents et d'homopolyamides aliphatiques pour la fabrication de pièces de formage transparentes
EP2857437A1 (fr) 2013-10-04 2015-04-08 Evonik Industries AG Mélange de polyamide
US9416233B2 (en) 2012-02-15 2016-08-16 Toray Industries, Inc. Composite polyamide fine particles and method of producing same
US20180100064A1 (en) 2016-10-12 2018-04-12 Ems-Patent Ag Glass filler-reinforced polyamide moulding compounds based on amorphous copolyamides
US20180327592A1 (en) 2015-11-17 2018-11-15 Arkema France Amorphous polyamide based composition exhibiting an improved dimensional stability
US11466153B2 (en) 2017-12-22 2022-10-11 Ems-Patent Ag Polyamide molding compound
US20230033437A1 (en) 2021-07-14 2023-02-02 Ems-Chemie Ag Transparent polyamides with good weathering resistance
CN117430947A (zh) 2023-11-17 2024-01-23 珠海万通特种工程塑料有限公司 一种耐化学、低内应力的聚酰胺复合材料及其制备方法和应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2460858A1 (fr) * 2010-12-02 2012-06-06 EMS-Patent AG Masses de formage polyamides à base de mélanges de copolyamides transparents et d'homopolyamides aliphatiques pour la fabrication de pièces de formage transparentes
US9416233B2 (en) 2012-02-15 2016-08-16 Toray Industries, Inc. Composite polyamide fine particles and method of producing same
EP2857437A1 (fr) 2013-10-04 2015-04-08 Evonik Industries AG Mélange de polyamide
EP2857437B1 (fr) * 2013-10-04 2019-06-19 Evonik Degussa GmbH Mélange de polyamide
US20180327592A1 (en) 2015-11-17 2018-11-15 Arkema France Amorphous polyamide based composition exhibiting an improved dimensional stability
US20180100064A1 (en) 2016-10-12 2018-04-12 Ems-Patent Ag Glass filler-reinforced polyamide moulding compounds based on amorphous copolyamides
US11466153B2 (en) 2017-12-22 2022-10-11 Ems-Patent Ag Polyamide molding compound
US20230033437A1 (en) 2021-07-14 2023-02-02 Ems-Chemie Ag Transparent polyamides with good weathering resistance
CN117430947A (zh) 2023-11-17 2024-01-23 珠海万通特种工程塑料有限公司 一种耐化学、低内应力的聚酰胺复合材料及其制备方法和应用

Also Published As

Publication number Publication date
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