WO2005000953A2 - Matiere polyamide a mouler, procede pour produire la matiere polyamide a mouler, et pieces moulees a partir de la matiere polyamide a mouler - Google Patents

Matiere polyamide a mouler, procede pour produire la matiere polyamide a mouler, et pieces moulees a partir de la matiere polyamide a mouler Download PDF

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Publication number
WO2005000953A2
WO2005000953A2 PCT/EP2004/006852 EP2004006852W WO2005000953A2 WO 2005000953 A2 WO2005000953 A2 WO 2005000953A2 EP 2004006852 W EP2004006852 W EP 2004006852W WO 2005000953 A2 WO2005000953 A2 WO 2005000953A2
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WO
WIPO (PCT)
Prior art keywords
polyamide
molding composition
composition according
polyamide molding
additive
Prior art date
Application number
PCT/EP2004/006852
Other languages
German (de)
English (en)
Other versions
WO2005000953A3 (fr
Inventor
Eduard Schmid
Heinz Hoff
Original Assignee
Ems-Chemie-Ag
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 Ems-Chemie-Ag filed Critical Ems-Chemie-Ag
Publication of WO2005000953A2 publication Critical patent/WO2005000953A2/fr
Publication of WO2005000953A3 publication Critical patent/WO2005000953A3/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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • Polyamide molding compound process for producing the polyamide molding compound and moldings which can be produced from the polyamide molding compound
  • the invention relates to a novel polyamide molding composition which contains a hydroxyl-functionalized, sterically hindered amine as an additive.
  • the invention further relates to a method for producing such a molding compound and molded parts that can be produced with this molding compound.
  • thermoplastic molding compositions In practice, the most varied requirements are placed on the material properties of thermoplastic molding compositions.
  • Polyamides have high strength values and are particularly resistant to fuels, greases and oils.
  • PA12 and PA11 are used for fuel, hydraulic and compressed air brake lines.
  • N-alkylbenzene and toluenesulfonamides are particularly suitable as plasticizers.
  • plasticizers such as thermoplastic molding composition is described, for example, in EP 0 388 583 B1.
  • the handling of such plasticizers and in particular their incorporation into polyamide molding compositions is associated with difficulties.
  • the most commonly used plasticizer in this class N-butylbenzenesulfonamide (BBSA)
  • BBSA N-butylbenzenesulfonamide
  • this plasticizer is volatile, toxic and environmentally hazardous. Plasticizers of this type are therefore not only to be incorporated into the polyamide molding composition in terms of their handling, ie especially when they are incorporated, but also because of the toxicity there is also an environmental hazard.
  • polyamide molding compositions there is therefore a great need for polyamide molding compositions to find an additive which does not have the above-described negative properties of the previously known plasticizers and which at the same time has further positive effects on the polyamide molding composition in relation to the rheological properties. Furthermore, it is an object of the present invention to provide a corresponding method for producing such a polyamide molding compound and the corresponding molded parts.
  • the object is achieved in relation to the polyamide molding compound by the features of claim 1, in relation to the method for producing the polyamide molding compound by the features of patent claim 15 and in relation to the molded parts by the features of claim 21.
  • the subclaims show partial further training.
  • the polyamide molding composition based on the molding composition, comprises 30-99% by weight of a thermoplastic polyamide and 0.1-30% by weight of an additive of the general formula I
  • polyamide molding composition according to the invention may contain further additives.
  • the advantage of the additive according to the invention can be seen in the fact that most of the compounds of the general formula I, as described above, are less volatile than the compounds of the prior art. This has the advantage that both when incorporated into the polyamide molding compound and No processing of smoke and odors occurs during processing by injection molding or extrusion and no loss of the compound of formula I occurs during drying. Surprisingly, it was also found that polyamide molding compositions which contain such an additive have excellent processability in injection molding and extrusion processes because they have a high flowability. The additive in the formulation according to the invention thus also has the function of a processing aid.
  • the additive of the polyamide molding composition according to the invention is basic, but the two nitrogen atoms are sterically completely shielded, they cannot have a chain-splitting effect. It can therefore be assumed that the carboxyl end acid groups are deprotonated and thus the acid groups that are mainly responsible for the hydrolytic degradation are no longer present as such. This has to
  • the molding compositions which contain the additive according to the invention have a significantly improved hydrolysis stability compared to polyamide molding compositions which contain the compounds of the prior art.
  • the additive of the general formula I is also capable of hydrogen bonding, as is already present in large numbers in the polyamide. This obviously has a positive effect on its compatibility with polyamide.
  • Pentrol is the addition product of propylene oxide to diethylene triamine. Because of its additional hydroxyl group and higher molecular weight, Pentrol is even less volatile than Quadrol.
  • Preferred addition amounts for the compound of general formula I are 0.3 to 20, particularly preferably 0.5 to 15% by weight.
  • thermoplastic molding compositions can be improved further if, in addition to the additive described above, a plasticizer known per se from the prior art in a weight ratio of 0-30% by weight, based on the molding composition is added.
  • the additional plasticizers are preferably selected so that they likewise have a low solidification point and, in particular when mixed with the additive according to the invention, results in a low solidification temperature.
  • the invention naturally also includes the use of other plasticizers known from the prior art, which can be used for polyamide molding compositions.
  • the polyamide molding composition according to the invention can contain further additives known in polyamide in a proportion by weight of 0.50-60% by weight.
  • processing aids and / or stabilizers can also be added to the polyamide molding composition.
  • processing aids and stabilizers are known from the prior art.
  • the molding composition according to the invention can thus contain thermoplastic polyamides as they are known per se in the prior art.
  • C 1 -C 2 lactams and / or C 6 -C 12 aminocarboxylic acids can be used as polyamide-forming monomers.
  • linear and cyclic, aliphatic and aromatic dicarboxylic acids, linear and cyclic, aliphatic diamines and corresponding salts of diamines and dicarboxylic acids can be used as polyamide-forming monomers for the production of the thermoplastic polyamide which is suitable for the polyamide molding composition according to the invention.
  • polyamide-forming monomers C 4 -C 44 dicarboxylic acids, such as. B. azelaic acid TPS, IPS and / or naphthalene dicarboxylic acid and C 2 -C 2 diamines can be used.
  • polyamides are: PA46, PA66, PA68, PA69, PA610, PA612, PA410, PA810, PA1010, PA412, PA1012, PA1212, PA6, PA7, PA8, PA9, PA10, PAH and PA12.
  • the polyamide molding compound can of course also contain alloys and / or mixtures of polyamides.
  • Other components that can be added to the polyamide mixture are impact modifiers, flame retardants such as. B. melamine cyanurate, melamine phosphate, magnesium hydroxide, halogen-containing flame retardants and phosphorus-containing compounds, as well as reinforcing agents and additives to increase the dimensional stability with z.
  • the invention further relates to a method for producing a polyamide molding composition described above.
  • the polyamide molding composition is produced in such a way that either a mixture of the additive, e.g. with water, with the aid of a nozzle, onto the finely divided, solid form polyamides and then the mixture is circulated and dried or that a direct incorporation into the polyamide melt is carried out.
  • the additive in which the additive is incorporated directly into the melt, it is advantageous if it is diluted with water (5-10% water) and then injected into the polyamide melt during the extrusion run.
  • the polyamide can already contain additives or these can be incorporated into the polyamide melt at the same time as the additive.
  • the additive can also be combined with other plasticizing compounds the polyamide melt can be incorporated.
  • the invention also relates to molded parts which have been produced from the polyamide molding compositions described in more detail above.
  • molded parts are pipes, fibers, jackets, injection molded parts and foils.
  • LV. the relative solution viscosity, measured on a 0.5 percent m-cresol solution
  • MVI volume flow index (Melt Volume Index) according to ISO 1133 in the unit of measured [cm 3/10 min.] At 275 ° C, kg and a load of 5 after a melting time of 4 minutes.
  • Quadrol L brand name of BASF AG, Ludwigshafen, DE
  • Quadrol L When delivered, Quadrol L is an extraordinarily highly viscous liquid that is not easily pumpable through standard piping systems. However, their fluidity can be reduced to a limited extent by increasing the temperature. The addition of water results in a significantly greater reduction in viscosity. For example, the viscosity according to EN 12092 drops from 81000 mPas to only 3150 mPas by adding only 10% by weight of water. Comparative experiment 1 (W 1) and experiment 2 (V2)
  • Quadrol L To incorporate Quadrol L into the same PA12 melt, it was diluted to 90% with water and the mixture was then heated to 80 ° C. In this state, the mixture was extremely pumpable and, as in comparative experiment 1, was easy to meter into the PA melt. Despite the water content in the Quadrol, a colorless, transparent and bubble-free strand resulted at the nozzle. In particular, no disturbing vapors were found when Quadrol was incorporated.
  • the formulations each contain an additional 0.5% of Irganox 1098 as a heat stabilizer, and in test 6 5% and in test 7 10% zinc ionomer (Surlyn 9320) are also used as impact modifiers.
  • the process conditions were chosen identical to Wl and V2.
  • the recipes and the essential test conditions are summarized in Table 1. In this mean + a very good, o a good and - an unsatisfactory result.
  • test tubes with a diameter of 8 mm and a wall thickness of 1 mm 8xl tubes were produced from the granules from tests V3, V6 and V7 on an extrusion system with a single-screw screw which is common for the production of PA12 tubes .
  • An excellent extrusion behavior of these formulations was shown, whereby melt temperatures of only approx. 230 to 240 ° C were sufficient for the production of translucent, dimensionally stable and inscribable tubes with a smooth surface. When these pipes are stored, there is no bleeding effect.
  • Another important result is that no annoyance caused by released plasticizer vapors was found, as is the case with the formulation in accordance with comparative test W1.
  • Table 1 Summary of the recipes and properties of test examples V3 to V7
  • test tubes according to Table 2 were subjected to the tests customary for fuel lines.
  • W8 corresponds to a standard PA12 formulation softened with 12% BBSA.
  • Table 2 Summary of the recipes and properties of the experimental examples V9 and V10 and the comparative example W8
  • This formulation is used in the follow-up experiments and is called Materbatch MB1.
  • Materbatch MB1 By the incorporation of Quadrol L MVI from 120 to 370 cm 3/10 min is. elevated.
  • PA12 from test V5, containing 20% Quadrol L. This product is called MB2 below.
  • the addition of the high proportion of Quadrol causes a very significant increase in the MVI of 20 to 370 cm 3/10 min.
  • Table 3 Polyamide-Quadrol blends; the quadrol concentration is 1.0 wt.
  • G21 is an amorphous polyamide made from isophthalic acid, terephthalic acid and hexamethylene diamine
  • ELX 2112 is a block polymer made from PA6 and polyether segments
  • Grilon F40 is a highly viscous PA6
  • ELY 60 is a PA12 elastomer with a polytetrahydrofuran soft segment. In all cases, this resulted in smooth, bubble-free extrusion strands and in no case did sweat-out effects occur which would indicate that the polyamide was incompatible with the Quadrol. With transparent polyamide G21, the transparency is not affected by the addition of the masterbatch.
  • the measured MVI values impressively demonstrate that Quadrol L significantly increases the melt flow of the different polyamides.
  • 5% MB2 was extruded into the transparent commercial product of EMS-CHEMIE AG, Grilamid TR 55, at 270 ° C.
  • the formulation could be in the injection molding process to excellent transparent test specimens, and the MVI, measured as usual at 275 ° C increased from 15 for the pure polyamide to 23 cm 3/10 min.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne une nouvelle matière polyamide à mouler qui contient en tant qu'additif une amine à encombrement stérique à fonction hydroxyle. L'invention a également pour objet un procédé pour produire une matière à mouler de ce type, et des pièces moulées à partir de cette matière à mouler.
PCT/EP2004/006852 2003-06-27 2004-06-24 Matiere polyamide a mouler, procede pour produire la matiere polyamide a mouler, et pieces moulees a partir de la matiere polyamide a mouler WO2005000953A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10329110A DE10329110A1 (de) 2003-06-27 2003-06-27 Polyamidformmasse, Verfahren zur Herstellung der Polyamidformmasse und Formteile herstellbar aus der Polyamidformmasse
DE10329110.5 2003-06-27

Publications (2)

Publication Number Publication Date
WO2005000953A2 true WO2005000953A2 (fr) 2005-01-06
WO2005000953A3 WO2005000953A3 (fr) 2005-03-17

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DE (1) DE10329110A1 (fr)
WO (1) WO2005000953A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1550696A1 (fr) * 2003-12-30 2005-07-06 EMS-Chemie AG Masses à mouler thermoplastiques à base de polyamide
EP1550684A2 (fr) * 2003-12-30 2005-07-06 EMS-Chemie AG Utilisation de compositions de moulage à base de polyamide présentant une formation réduite de dépôts solides
WO2006122602A1 (fr) * 2005-05-20 2006-11-23 Ems-Chemie Ag Matieres a mouler en polyamide presentant des proprietes rheologiques ameliorees, leur production et leur utilisation
US7786222B2 (en) 2005-05-20 2010-08-31 Ems-Chemie Ag Polyamide oligomers and their use
CN103642231A (zh) * 2013-11-18 2014-03-19 安徽宜万丰电器有限公司 一种汽车塑料件用耐磨改性尼龙材料
EP2060607B1 (fr) 2007-11-16 2017-01-18 Ems-Patent Ag Composition à mouler chargée à base de polyamide

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469542A2 (fr) * 1990-08-02 1992-02-05 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
EP0591731A1 (fr) * 1992-09-24 1994-04-13 BASF Aktiengesellschaft Masses à mouler en polyamide fluides
DE4311885A1 (de) * 1993-04-10 1994-12-01 Huels Chemische Werke Ag Polyamid-Formmassen mit verbesserter Wärmestabilität bei der Herstellung und Verarbeitung
WO1995022577A1 (fr) * 1994-02-16 1995-08-24 E.I. Du Pont De Nemours And Company Polyamides aux caracteristiques chromatiques ameliorees et plus faciles a traiter, et procede de fabrication
EP0801091A1 (fr) * 1995-10-27 1997-10-15 Mitsui Petrochemical Industries, Ltd. Polyamide semi-aromatique, procede de production et composition contenant ce polyamide
EP1182228A1 (fr) * 2000-08-21 2002-02-27 Mitsubishi Gas Chemical Company, Inc. Composition de résine polyamide
US20020193478A1 (en) * 2001-04-26 2002-12-19 Helmut Schulte Polyamide molding compositions for producing transparent films
EP1354906A1 (fr) * 2002-04-19 2003-10-22 Mitsubishi Gas Chemical Company, Inc. Résine de polyamide

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3237401A1 (de) * 1982-10-08 1984-04-12 Bayer Ag, 5090 Leverkusen Schlagzaehe polyamide
DE4426004A1 (de) * 1994-07-22 1996-01-25 Basf Ag Verfahren zum optischen Aufhellen von Polyamiden

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0469542A2 (fr) * 1990-08-02 1992-02-05 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
EP0591731A1 (fr) * 1992-09-24 1994-04-13 BASF Aktiengesellschaft Masses à mouler en polyamide fluides
DE4311885A1 (de) * 1993-04-10 1994-12-01 Huels Chemische Werke Ag Polyamid-Formmassen mit verbesserter Wärmestabilität bei der Herstellung und Verarbeitung
WO1995022577A1 (fr) * 1994-02-16 1995-08-24 E.I. Du Pont De Nemours And Company Polyamides aux caracteristiques chromatiques ameliorees et plus faciles a traiter, et procede de fabrication
EP0801091A1 (fr) * 1995-10-27 1997-10-15 Mitsui Petrochemical Industries, Ltd. Polyamide semi-aromatique, procede de production et composition contenant ce polyamide
EP1182228A1 (fr) * 2000-08-21 2002-02-27 Mitsubishi Gas Chemical Company, Inc. Composition de résine polyamide
US20020193478A1 (en) * 2001-04-26 2002-12-19 Helmut Schulte Polyamide molding compositions for producing transparent films
EP1354906A1 (fr) * 2002-04-19 2003-10-22 Mitsubishi Gas Chemical Company, Inc. Résine de polyamide

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1550696A1 (fr) * 2003-12-30 2005-07-06 EMS-Chemie AG Masses à mouler thermoplastiques à base de polyamide
EP1550684A2 (fr) * 2003-12-30 2005-07-06 EMS-Chemie AG Utilisation de compositions de moulage à base de polyamide présentant une formation réduite de dépôts solides
EP1550684A3 (fr) * 2003-12-30 2006-07-05 EMS-Chemie AG Utilisation de compositions de moulage à base de polyamide présentant une formation réduite de dépôts solides
US7312263B2 (en) 2003-12-30 2007-12-25 Ems-Chemie Ag Thermoplastic polyamide moulding compositions
WO2006122602A1 (fr) * 2005-05-20 2006-11-23 Ems-Chemie Ag Matieres a mouler en polyamide presentant des proprietes rheologiques ameliorees, leur production et leur utilisation
EP1983029A3 (fr) * 2005-05-20 2008-11-05 Ems-Patent Ag Boîtier composé d'une masse de formage en polyamide dotée d'une fluidité améliorée, sa fabrication et son utilisation
US7786222B2 (en) 2005-05-20 2010-08-31 Ems-Chemie Ag Polyamide oligomers and their use
US7910652B2 (en) 2005-05-20 2011-03-22 Ems-Chemie Ag Polyamide molding materials with an improved flowability, the production thereof and its use
US8138259B2 (en) 2005-05-20 2012-03-20 Ems-Chemie Ag Polyamide molding materials with an improved flowability, the production thereof and its use
EP2060607B1 (fr) 2007-11-16 2017-01-18 Ems-Patent Ag Composition à mouler chargée à base de polyamide
CN103642231A (zh) * 2013-11-18 2014-03-19 安徽宜万丰电器有限公司 一种汽车塑料件用耐磨改性尼龙材料

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Publication number Publication date
DE10329110A1 (de) 2005-02-03
WO2005000953A3 (fr) 2005-03-17

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